Soft thermoplastic resin composition

ABSTRACT

A soft thermoplastic resin composition comprising: 
     100 parts by weight of a resin component (A) containing 15 to 65 parts by weight of a vinyl chloride resin having a degree of polymerization of 2000 or less, and 35 to 85 parts by weight of a polyhydroxyalkanoate; and 0.1 to 8 parts by weight of a resin component (B) which is one or more resins selected from the group consisting of a (meth)acrylate resin and an acrylonitrile-styrene resin, and has a weight average molecular weight, in terms of the polystyrene, of 400,000 or more.

TECHNICAL FILED

The present invention relates to a soft thermoplastic resin composition,which is alloy mainly containing a vinyl chloride resin and apolyhydroxyalkanoate.

BACKGROUND ART

In order to protect the global environment, low environmental loadmaterials have been received attention, which have a low dependence onfossil fuels which are exhaustible resources and generate large amountsof carbon dioxide and air pollutants. Many low environmental loadmaterials are known, and typical examples thereof may include polylacticacid, polyhydroxyalkanoates, polyamide 11, and the like. The vinylchloride resin is also a low environmental load material, because 57%thereof is derived from a salt and it has a low dependence on fossilfuels; it has excellent mechanical properties and durability; and thehardness can be widely adjusted to ranges from hard to soft by additionof a plasticizer. The vinyl chloride resin, accordingly, have recentlyreceived attention again.

A soft vinyl chloride resin has the excellent mechanical properties anddurability, but has a problem in which a large amount of a plasticizeris added. The plasticizer has not only defects of physical propertiessuch as high plasticizer migration, bleeding out property, andvolatility but also a defect in which a material suspected of being anenvironmental hormone is used as the plasticizer, and thus recently theimprovement, thereof has been advanced.

For example, polyester plasticizers whose molecular weight is increasedto about several thousands to the first half of about several tens ofthousands, classified into an oligomer, are known, although usually usedplasticizers have a molecular weight of about several hundreds. Theplasticizers above, however, cannot sufficiently reduce the plasticizermigration, the bleeding out property, and the volatility, and many ofthem have a problem in which they are derived from fossil fuels.

Patent Document 1 suggests a resin composition containing apolyhydroxyalkanoate oligomer and a vinyl chloride resin, but it has noExamples in which the vinyl chloride resin is used, and sufficienttensile elasticity and tensile elongation cannot be obtained in otherExamples. In addition, polyhydroxyalkanoate oligomers having a molecularweight of 25000 or less are mainly used, and such oligomers haveproblems of the comparatively high plasticizer migration, bleeding-outproperty, and volatility, as with the polyester plasticizer, because ofthe comparatively small molecular weight of the oligomer.

On the other hand, Patent Document 2 is an example in which excellentcompatibility with the vinyl chloride resin is realized while themolecular weight is as high as a resin, i.e., from the latter half ofseveral tens of thousands to several hundreds of thousands; whichdiscloses a copolyester polymer containing long chain ester unitsderived from a long chain glycol having a molecular weight of 600 to6000 and a dicarboxylic acid having a molecular weight of less than 300,and short chain ester units derived from a diol having a molecularweight of less than 250 and a dicarboxylic acid having a molecularweight of less than 300.

The copolyester polymer described above has a sufficient high molecularweight, and thus has the low plasticizer migration, bleeding outproperty, and volatility, but its starting materials are derived fromfossil fuels, and further improvements are required. In addition, PatentDocument 2 has neither description of transparency nor uses whichrequire the transparency at all, and thus it can be considered that thetransparency of the copolyester polymer may be insufficient.

On the other hand, Patent Document 3 discloses a resin compositioncontaining a vinyl chloride resin, a polyester resin, and an acrylicpolymer. Patent Document 3 is a technique directed to a fiber havingincreased heat-resistance by improving a thermal shrinkage upon asecondary processing, and a melting paint of the polyester resin is setso that it can impart the excellent heat-resistance in a formingtemperature range of the vinyl chloride resin, whereby the comparativelybetter heat-resistance at the melting point can be realized after themolding. However, the polyester resins actually used in Patent Document3, such as a polylactic acid resin and a crystalline polyester resin,are not suitable for softening the vinyl chloride resin.

CITATION LIST Patent Literatures

Patent Document 1: JP-T No. H08-503723

Patent Document 2: JP-A No. S48-751

Patent Document 3: JP-A No, 2008-144095

SUMMARY OF INVENTION Technical Problem

The present invention, aims at providing a soft thermoplastic resincomposition, which is a low environmental load material having a lowdependence on fossil fuels capable of easily generating carbon dioxideand air pollutants, in order to protect the global environment; whichcontains no plasticizer suspected of being an environmental hormone, aswith a soft vinyl chloride resin; which has a reduced plasticizermigration, while it has the mechanical properties as good as those ofthe soft vinyl chloride resin; and which has an excellentmold-processability.

Solution to Problem

In order to solve the problems described above; the present inventorshave repeated a painstaking study. As a result, they have found when apolyhydroxyalkanoate, a specific (meth)acrylate resin, and anacrylonitrile-styrene resin are melt-mixed with a specific vinylchloride resin in a specific ratio to alloy them, a desired softthermoplastic resin composition can be obtained; and have, completed thepresent invention.

The present invention, accordingly, provides soft thermoplastic resincompositions 1) to 7), a molded article 8), and a film or a sheet 9).

1) A soft thermoplastic resin composition containing:

100 parts by weight of a resin component (A) containing 15 to 65 partsby weight of a vinyl chloride resin having a degree of polymerization of2000 or less, and 35 to 85 parts by weight of a polyhydroxyalkanoate;and 0.1 to 8 parts by weight of a resin component (B) which is one ormore resins selected from the group consisting of (meth)acrylate resinsand acrylonitrile-styrene resins having a weight average molecularweight, in terms of the polystyrene, of 400,000 or more.

The soft thermoplastic resin composition 1) above, accordingly, contains15 to 65 parts by weight of a vinyl chloride resin having a degree ofpolymerization of 2000 or less, and 35 to 85 parts by weight of apolyhydroxyalkanoate, the total amount thereof being 100 parts byweight, and 0.1 to 8 parts by weight, based on the total amount of 100parts, of one or more resins selected from the group consisting of a(meth)acrylate resin and an acrylonitrile-styrene resin, and has aweight average molecular weight, in terms of the polystyrene, of 400,000or more.

2) The soft thermoplastic resin composition according to 1) above,wherein the polyhydroxyalkanoate is a copolymer formed of monomer unitsderived from two or more kinds of hydroxyalkanoates.

3) The soft thermoplastic resin composition according to 2) above,wherein the copolymer contains monomer units derived from3-hydroxybutyrate and monomer units derived from hydroxyalkanoate otherthan 3-hydroxybutyrate. Here, the monomer unit derived from3-hydroxybutyrate is a bivalent group in which a hydrogen atom isremoved from a hydroxyl group in the 3-hydroxybutyrate and a hydroxylgroup is removed from a carboxyl group in the 3-hydroxybutyrate.Similarly, the monomer unit derived from hydroxyalkanoate is a bivalentgroup in which a hydrogen atom is removed from a hydroxyl group in thehydroxyalkanoate and a hydroxyl group is removed from a carboxyl groupin the hydroxyalkanoate.

4) The soft thermoplastic resin composition according to 3) above,wherein the hydroxyalkanoate other than 3-hydroxybutyrate is at leastone member selected from the group consisting of 4-hydroxybutyrate,3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, and3-hydroxydecanoate.

5) The soft thermoplastic resin composition according to 3) or 4) above,wherein the copolymer contains 50 to 95% by mole of monomer unitsderived from the 3-hydroxybutyrate.

6) The soft thermoplastic resin composition according to any one of 1)to 5) above, wherein the resin component (B) has a number averageprimary particle size of 40 μm or less.

7) The soft thermoplastic resin composition according to any one of 1)to 6) above, wherein a molded article therefrom having a thickness of 1mm has an HAZE of 50% or less.

8) A molded article comprising the soft thermoplastic resin compositionaccording to any one of 1) to 7).

9) A sheet or film comprising the molded article according to 8) above.

Advantageous Effects of Invention

The soft thermoplastic resin composition of the present invention is alow environmental load material containing fossil fuels in a low ratio,and has a softness and mechanical properties, which are almost the sameas those of a soft vinyl chloride resin, even if a plasticizer is notused, and, at the same time, has a reduced plasticizer migration, anexcellent mold-processability, and a high transparency.

DESCRIPTION OF EMBODIMENTS Soft Thermoplastic Resin Composition

The soft thermoplastic resin composition of the present invention (whichhereinafter may sometimes be referred to simply as “resin composition ofthe invention”) contains a resin component (A) containing a vinylchloride resin and a polyhydroxyalkanoate, and a resin component (B)which is at least one resin selected from the group consisting of(meth)acrylate resins and acrylonitrile-styrene resins having a weightaverage molecular weight, in terms of the polystyrene, of 400,000 ormore.

The present invention is characterized by softening the hard vinylchloride resin by using the polyhydroxyalkanoate, not using a largeamount of a plasticizer. The compatibility between the vinyl chlorideresin and the polyhydroxyalkanoate is excellent, and thus the vinylchloride resin can be efficiently softened, and a soft thermoplasticresin composition having an excellent transparency can be obtained.

The addition of the (meth)acrylate resin and the acrylonitrile-styreneresin not only promotes the gelation of the vinyl chloride resin andsolves problem such as air marks and flow marks, which are moldingfailures conflict with each other, in a well-balanced way particularlyin calendar molding, but also imparts flexibility to the molten resincomposition of the invention, whereby releasability from a calendar rollcan be improved.

As the major premise, about 60% of all vinyl chloride resins usuallyused are derived from salt, i.e., non-fossil fuels. In addition,polyhydroxyalkanoate is also completely derived from a non-fossil fuel.The resin composition of the invention, which mainly contains thecomponents above, has the high dependence of the non-fossil fuel, andthus it can be said that the composition of the invention is the lowenvironmental load material.

From the above, the soft thermoplastic resin composition having the lowenvironmental load, low plasticizer migration, excellent softness,excellent mold-processability, and excellent transparency is obtained.

In the present invention, “the composition is soft” means that thecomposition has a tensile elasticity of 1000 MPa or less and a tensileelongation of 100% or more. The resin composition of the invention issoft like a rubber, and thus the tensile test thereof should becompliant with JIS K 6251 “Rubber, vulcanized orthermoplastics—Determination of tensile stress-strain properties,” andit is preferable to use a No. 2 dumbbell as a test sample and to set atest speed at 500 mm/minute. The thickness of the test sample is notparticularly limited, and a thickness of 1 mm is recommended, becausethere are only a few variations and the measurement can be extremelyprecisely performed.

In the resin composition of the invention, it is preferable that amolded article therefrom having a thickness of 1 mm has an HAZE of 50%or less. When the HAZE is more than 50%, the transparency andcolorability are deteriorated, and thus the application thereof maypossibly be limited. In order to expand its application, the moldedarticle has an HAZE of preferably 40% or less, more preferably 30% orless, even more preferably 20% or less, particularly preferably 10% orless.

The resin composition of the invention can be applied to variousapplications including applications for the product in which soft vinylchloride resin is used, such as building materials, wire-coatingmaterials, generally used films and sheets, coatings, adhesives, andpigments, agricultural plastic sheets, leather, extruded products (hosesand gaskets), footwear, and compound sols, because of its excellentsoftness, mold-processability, and transparency.

Application examples of the building material may include interiormaterials such as wallpaper and flooring materials, water sealingmaterials such as waterproof sheets for civil engineering andconstruction works, and roofing sheets, tarpaulin, canvas, tents, airdomes, flexible containers, curing sheets, track sheets, and the like.

Application examples of the wire-coating material may include wireharnesses, power cords for tools, CV cables, unit cables for indoorwiring, flat cables, and the like.

Application examples of the generally used films and sheets may includeprinting materials, wrapping applications for clothing products,groceries, convenience goods, and stationeries, binding applications forpublications and magazines, covers for electric appliances and machines,commodities such as raincoats, umbrellas, and shopping bags, playequipment such as swimming rings and beach balls, nursing goods such asmarking films, Airpoline, and Rainbow Tunnel, health and fitnessproducts such as yoga mats, and the like.

Application examples of the leather may include furniture such as sofasand chairs, interior articles such as fancy cases, table clothes, tablecovers, and accordion curtains, interior materials for automobiles,fashion goods such as belts, bags, and suitcases, and the like.

Application examples of the extruded product (hose and gasket) mayinclude garden hoses, gaskets for a refrigerator, flexible hoses for awashing machine and a cleaner, specific hoses for industrial use whichare reinforced by an elastic spiral bellows hose or spring as a core,sealing materials (packing) utilized in a sliding window frame, sealingmaterials for an automobile window, and the like.

Application examples of the footwear may include footwear made from asynthetic material, sandals, slippers, Japanese sandals, rubber boots,injection boots, core materials for sandals, and the like.

Application examples of the coatings, adhesives, and pigments mayinclude coating film-forming aid for an emulsion coating, flexibilityimproving agent, adhesives for plywood in a corrugated carton orfurniture, additives such as toner, and the like. In addition, theapplication examples thereof may include medical applications, includingblood bags, tubes, and the like.

The resin composition of the invention has an extensive moldability,which can be molded in various molding methods, and thus molded articleshaving various shapes or states can be obtained therefrom. Inparticular, the composition is suitably molded in a calendar molding,and thus is preferable for a sheet or film application. In addition, ithas characteristics of the remarkably reduced plasticizer migration andof a small tack feeling because of no use of a plasticizer, and thus itcan be preferably used for printing materials such as a marking film. Inaddition, the molded articles obtained therefrom have an excellenttexture of an outside appearance, and high-grade sensation, and thus itcan be preferably used for fashion articles such as leather in expensivefurniture, belts, bags, and suitcases.

Hereinafter, the resin component (A) and the resin component (B) in theresin composition of the invention are explained in more detailed below.

<Resin Component (A)>

The resin component (A) contains a vinyl chloride resin having a degreeof polymerization of 2000 or less and a polyhydroxyalkanoate, preferablyconsists of the vinyl chloride resin having a degree of polymerizationof 2000 or less and the polyhydroxyalkanoate.

As the vinyl chloride resin, any known vinyl chloride resin having adegree of polymerization of 2000 or less may be used without anylimitation, and it is possible to preferably use polymers containing 60%by weight to 100% by weight of a vinyl chloride monomer derived from atleast one monomer compound selected from the group consisting of vinylchloride and vinyl chloride derivatives, and 0 to 40% by weight of amonomer copolymerizable with the vinyl chloride monomer (which ishereinafter referred to as “arbitrary monomer (1)”), the total amountthereof being 100% by weight. When the content of the vinyl chloridemonomer is less than 60% by weight or the content of the arbitrarymonomer (1) is more than 40% by weight, the compatibility, themechanical properties, and the like, which are original properties ofthe vinyl chloride resin, may sometimes be lost.

In terms of the same viewpoint as above, i.e., the improvement of thecompatibility, the mechanical properties, and the like, the vinylchloride resin used in the present invention is preferably a polymercontaining 75% by weight to 100% by weight of the vinyl chloride monomerand 0 to 25% by weight of the arbitrary monomer (1), more preferably apolymer containing 85% by weight to 100% by weight of the vinyl chloridemonomer and 0 to 15% by weight of the arbitrary monomer (1).

The vinyl chloride derivative is preferably a compound having astructure in which 1, 2, or 3 hydrogen atoms in the vinyl chloride aresubstituted by chlorine atoms, more preferably a compound having astructure in which 1 or 2 hydrogen atoms in the vinyl chloride aresubstituted by chlorine atoms, and even more preferably, a compoundhaving a structure in which one hydrogen atom in the vinyl chloride issubstituted by a chlorine atom. It becomes difficult to advance thegelation as the number of hydrogen atoms in the vinyl chloridesubstituted by the chlorine atoms is increased, and the mold-processingmay not sometimes be performed. Even if the gelation can be performed,the melt-viscosity of the resulting product is too high to obtain themolded article having the desired shape, or the molding failures such asflow marks may sometimes be generated.

Any known substance may be used as the arbitrary monomer (1), and it ispreferable to use, for example, one or more compounds selected from thegroup consisting of (meth)acrylates, vinyl arenes, vinylcarboxylicacids, vinyl cyanides, vinyl halides excluding vinyl chloride, vinylacetate, alkenes, and alkynes.

The (meth)acrylates may include, for example, methacrylate having analkyl group with 1 to 22 carbon atoms, such as methyl methacrylate,ethyl methacrylate, propyl methacrylate, butyl methacrylate,2-ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate,stearyl methacrylate, and behenyl methacrylate; acrylates having analkyl group with 1 to 22 carbon atoms and a hydroxyl group, such as2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate; (meth)acrylateshaving an epoxy group such as glycidyl (meth)acrylate; (meth)acrylateshaving an alkyl group with 1 to 22 carbon atoms and an alkoxy group, andthe like. The number of carbon atoms of the alkyl group in the(meth)acrylate is not necessarily limited; however, for example, if thenumber of carbon atoms is more than 22, the polymerizablity maysometimes be deteriorated, and thus it is possible to preferably use the(meth)acrylates having an alkyl group with 22 or less carbon atoms. Inorder to further improve the polymerizablility; (meth)acrylates havingan alkyl group with 12 or less carbon atoms are more preferable, and(meth)acrylates having an alkyl group with 8 or less carbon atoms areeven more preferable, because they have the excellent compatibility withthe polyhydroxyalkanoate.

The vinyl arenes may include styrene, α-methyl styrene,monochlorostyrene, dichlorostyrene, and the like. The vinylcarboxylicacids may include acrylic acid, methacrylic acid, itaconic acid, and thelike. The vinyl cyanides may include acrylonitrile, methacrylonitrile,and the like. The vinyl halides excluding vinyl chloride may includevinyl bromide, vinyl fluoride, and the like. The alkenes may includeethylene, propylene, butene, butadiene, isobutene, and the like. Thealkynes may include acetylene and the like.

Of the arbitrary monomers (1) described above, at least one monomerselected from the group consisting of the alkyl (meth)acrylates, vinylacetate, and alkenes is more preferable, in terms of the reactivity andsoftening; one or more monomers selected from the group consisting ofthe alkyl acrylate, vinyl acetate, and ethylene are even morepreferable; and vinyl acetate is particularly preferable in terms of thereactivity, softening, versatility, and polymerizability. The vinylchloride monomers or the arbitrary monomers (1) in the vinyl chlorideresin may be used alone or as a mixture of two or more kinds.

The vinyl chloride resin, has a degree of polymerization of 2000 orless, whereby the good mold-processability can be imparted to, forexample, the vinyl chloride resin and, eventually, the resin compositionof the invention. When the degree of polymerization is more than 2000,the vinyl chloride resin is insufficiently melted and gelled, and thusit may be difficult to mold it. Even if the vinyl chloride resin can bemelted and kneaded, the melt-viscosity is too high to obtain the moldedarticle having the desired shape, or the molding failures such as flowmarks may sometimes be generated.

Although the resin composition of the invention can contain theplasticizer in a range in which a plasticizer migration is not so high,as described below, when the composition does not contain theplasticizer or contains the plasticizer in an amount of 5 parts byweight or less based on 100 parts by weight of the resin component (A),the vinyl chloride resin has preferably a degree of polymerization of1400 or less in terms of the easy molding, more preferably 1100 or less,even more preferably 900 or less because even if the composition doesnot contain the plasticizer, the molded article having the excellenttransparency can be obtained.

When the plasticizer is added in an amount of more than 5 parts byweight, the sufficient processability and transparency can be expressedeven if the degree of polymerization is higher, and the degree ofpolymerization of the vinyl chloride resin is preferably from 800 to1700, more preferably from 950 to 1400 because the excellent mechanicalproperties and the excellent mold-processability of vinyl chloride resincan be well-balanced.

In the resin composition of the invention, the vinyl chloride resin issoftened by the polyhydroxyalkanoate, and thus the vinyl chloride resinin the present invention has a glass transition temperature ofpreferably 130° C. or lower, more preferably 110° C. or lower, even morepreferably 90° C. or lower, particularly preferably 80° C. or lower.When the glass transition temperature is higher than 130° C. the vinylchloride resin cannot be sufficiently softened by thepolyhydroxyalkanoate alone and a large amount of plasticizer isnecessary in addition to the polyhydroxyalkanoate, and thus thesoftening and the low plasticizer migration may not sometimes beattained in a well-balanced way in the resin composition of theinvention.

The glass transition temperature (which hereinafter may sometimes bereferred to as “Tg”) of the vinyl chloride resin can be measured, forexample, by a differential scanning calorie analysis or a dynamicviscoelasticity measurement, but in the present invention the glasstransition temperature is a value calculated from a Fox formula usingvalues described in Polymer Hand Book (J. Brandrup, Interscience 1989).For example, 84° C. is used for the polyvinyl chloride Polyvinyl acetatehas a Tg of 32° C.

When Tg is measured according to the differential scanning calorieanalysis or the dynamic viscoelasticity measurement, as for at least thevinyl chloride resin, and a (meth)acrylate resin and anacrylonitrile-styrene resin described below, it is necessary to optimizemeasurement conditions so as to obtain values described in Polymer HandBook, because the Tg varies depending on the shape of a test sample tobe measured, the temperature-rising rate, and the like.

The vinyl chloride resin can be produced in a known method. Examplesthereof may include an emulsion polymerization, a microsuspensionpolymerization, a suspension polymerization, a solution polymerization,a bulk polymerization, and the like. The emulsion polymerization, themicrosuspension polymerization, and the suspension polymerization aremore preferable, because a powdery product characteristic, which can beeasily handled, can be obtained, and the suspension polymerization isparticularly preferable in terms of the versatility, in particular.

In the present invention, the vinyl chloride resin, obtained by thepolymerization, may be further modified. Typical example of themodification after the polymerization in the present invention mayinclude “chlorination.”

Of the vinyl chloride resins having a degree of polymerization of 2000or less, homopolymers of vinyl chloride and copolymers of vinyl chlorideand vinyl acetate are preferable. Of the homopolymers, homopolymershaving a degree of polymerization of 700 to 1500 are preferable, andhomopolymers having a degree of polymerization of 750 to 1400 are morepreferable. Of the copolymers, copolymers having a vinyl acetate contentof 5 to 15% by weight of the copolymer and copolymers having a degree ofpolymerization of 500 to 800 are preferable, and copolymers having avinyl acetate content of 5 to 15% by weight of the copolymer and adegree of polymerization of 500 to 800 are more preferable.

The polyhydroxyalkanoate, used together with the vinyl chloride resin inthe resin component (A), is a polymer having monomer units derived fromthe hydroxyalkanoate (bivalent groups in which the hydrogen atom isremoved from the hydroxyl group in the hydroxyalkanoate and the hydroxylgroup is removed from the carboxyl group in the hydroxyalkanoate). Themonomer units may include monomer units represented by the formula:[—CH(R)—CH₂CO—O—] wherein R is an alkyl group represented by—C_(n)H_(2n+1), and n is an integer of 1 to 24; monomer unitesrepresented by the formula: [—CH(R′)—CH₂—CH₂CO—O-] wherein R′ is H or analkyl group represented by —C_(n)H_(2n+1), and n is an integer of 1 to24, and the like. The monomer units may be used as alone or as a mixtureof two or more kinds. The homopolymer formed of only one kind can beexemplified by poly(3-hydroxybutyrate), and the like. In thehomopolymers, however, the degree of crystallinity is excessivelyincreased and the crystallization speed becomes too fast, and thuscrystals may sometimes be partly formed in the molded article. When thecrystals are formed in the molded article, there are parts whoserefractive index is different from those of other parts; as a result,the softness and the transparency of the molded article may sometimes bedeteriorated. For that reason, as the polyhydroxyalkanoate, copolymersformed of two or more kinds of monomer units are preferable. As thepolyhydroxyalkanoate, copolymers of monomer units derived from3-hydroxybutyrate and monomer units derived from hydroxyalkanoate otherthan the above are more preferable, from the viewpoints of the easyavailability of the starting materials, versatility, and theproductivity of the polymer.

The hydroxyalkanoate other than 3-hydroxybutyrate is not particularlylimited, and specific examples thereof may include 4-hydroxybutyrate,3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyoctanoate,3-hydroxydecanoate, and the like, in terms of the softness, thetransparency, and the like of the resin composition of the invention.

Specific examples of the copolymer of 3-hydroxybutyrate and the otherhydroxyalkanoate may includepoly[(3-hydroxybutyrate)-co-(4-hydroxybutyrate)],poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)],poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)],poly[(3-hydroxybutyrate)-co-(3-hydroxyoctanoate)],poly[(3-hydroxybutyrate)-co-(3-hydroxydecanoate)], and the like. Ofthese polymers, the poly[(3-hydroxybutyrate)-co-(4-hydroxybutyrate)],and poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] are preferable,because the softness can be easily imparted to the resin composition ofthe invention; and the poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)]is particularly preferable in terms of the softness and the transparencyof the resin composition of the invention.

In the copolymer described above, a copolymerization composition ratioof the monomer units derived from 3-hydroxybutyrate to the monomer unitsderived from hydroxyalkanoate other than the above (monomer unitsderived from 3-hydroxybutyrate/monomer units derived fromhydroxyalkanoate other than the above) is not particularly limited, andit is preferably from 50 to 95% by mole/5 to 50% by mole, morepreferably from 60 to 92% by mole/8 to 40% by mole, even more preferablyfrom 70 to 90% by mole/10 to 30% by mole, because the transparency andthe softness of the resin composition of the invention can be furtherincreased.

In the poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)], copolymers areparticularly preferable which have a ratio of the monomer units derivedfrom 3-hydroxybutyrate of 70 to 95% by mole of the copolymer, preferablyfrom 70 to 90% by mole, and a weight average molecular weight of 450.000to 600,000, preferably 500,000 to 550,000. In thepoly[(3-hydroxybutyrate)-co-(4-hydroxybutyrate)], copolymers areparticularly preferable which have a ratio of the monomer units derivedfrom 3-hydroxybutyrate of 70 to 95% by mole of the copolymer, preferably75 to 95% by mole, and a weight average molecular weight of 650,000 to1,150,000, preferably 700,000 to 1,050,000.

The polymerization method to obtain the copolymer described above is notparticularly limited, and any copolymerization method of a randomcopolymerization, an alternating copolymerization, a blockcopolymerization, and the like may be applied. The randomcopolymerization s preferable, because the degree of crystallinity ofthe obtained copolymer is reduced, the crystallization speed isdecreased, and the transparency is improved. The production method isnot particularly limited, and it is preferable to produce usingmicroorganisms.

The molecular weight of the polyhydroxyalkanoate is not particularlylimited, and it is preferably from 10,000 to 3,000,000, more preferablyfrom 30,000 to 2,000,000, even more preferably from 50,000 to 1,500,000,particularly preferably from 100,000 to 1,000,000, in terms of theimpact resistance, the tensile properties, and the mold-processabilityof the resin composition of the invention. When the polyhydroxyalkanoatehas a weight average molecular weight of less than 10,000, thepolyhydroxyalkanoate belongs to a class called an oligomer, and itsometimes may not be possible to suppress the plasticizer migration to alow level. In addition, the mechanical properties such as the strengthof the resin composition of the invention may sometimes be insufficient.On the other hand, when the weight average molecular weight is more than3,000,000, the mold-processability of the resin composition of theinvention may sometimes be reduced.

A method of measuring the weight average molecular weight of thepolyhydroxyalkanoate is not, particularly limited, and measurementmethods utilizing a gel permeation chromatography (GPC) are preferable.One example of the measurement methods is exemplified by a method inwhich chloroform is used as a mobile phase, a GPC system, manufacturedby Waters Corporation is used as a system, and Shodex K-804 (trade name,a polystyrene gel), manufactured by Showa Denko K. K., is used as acolumn filler. The weight average molecular weight can be obtainedaccording to the method in terms of the polystyrene.

A ratio of the vinyl chloride resin and the polyhydroxyalkanoate in theresin component (A) is that the vinyl chloride resin is from 0.15 to 65parts by weight and the polyhydroxyalkanoate is from 35 to 85 parts byweight, the total amount thereof being 100 parts by weight.

When the amount of the vinyl chloride resin is less than 15 parts byweight or the amount of the polyhydroxyalkanoate is more than 85 partsby weight, or when the amount of the vinyl chloride resin is more than65 parts by weight or the amount of the polyhydroxyalkanoate is lessthan 35 parts by weight, a non-soft resin composition sometimes may beobtained, for example, the softness is insufficient, the tensileelongation does not reach 100%. The non-soft resin composition can beused in hard applications, and the hard application may include, forexample, building materials such as window frames, sidings, decks, andthe like.

A blending ratio of the vinyl chloride resin and thepolyhydroxyalkanoate is preferably a ratio of 25 to 65 parts by weightof the vinyl chloride resin and 35 to 75 parts by weight of thepolyhydroxyalkanoate, more preferably a ratio of 35 to 65 parts byweight of the vinyl chloride resin and 35 to 65 parts by weight of thepolyhydroxyalkanoate because the excellent transparency can be obtained;even more preferably a ratio of 35 to 60 parts by weight of the vinylchloride resin and 40 to 65 parts by weight of the polyhydroxyalkanoatebecause the excellent softness can be obtained; still even morepreferably a ratio of 40 to 60 parts by weight of the vinyl chlorideresin and 40 to 60 parts by weight of the polyhydroxyalkanoate,particularly preferably a ratio of 40 to 55 parts by weight of the vinylchloride resin and 45 to 60 parts by weight of the polyhydroxyalkanoatebecause the resin composition of the invention having the transparency,the softness, the mold-processability, the plasticizer migration, andthe like in a well-balanced way at a high level can be obtained.

A more preferable combination of the vinyl chloride resin and thepolyhydroxyalkanoate is exemplified by a combination of at least onemember selected from the group consisting of “vinyl chloridehomopolymers having a degree of polymerization of 2000 or less, 700 to1500, or 750 to 1400” and “vinyl chloride copolymer containing vinylchloride and vinyl acetate, having a vinyl acetate content of 5 to 15%by weight of the copolymer, and having a degree of polymerization of 500to 800”; and at least one member selected from the group consisting of“poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] having a3-hydroxybutyrate content of 70 to 95% by mole, or 70 to 90% by mole ofthe copolymer, and a weight average molecular weight of 450,000 to600,000, or 500,000 to 550,000” and“poly[(3-hydroxybutyrate)-co-(4-hydroxybutyrate)] having a3-hydroxybutyrate content of 70 to 95% by mole, or 75 to 95% by mole ofthe copolymer, and a weight average molecular weight of 650,000 to1150,000 or 700,000 to 1050,000.”

<Resin Component (B)>

In the resin composition of the invention, as the resin component (B),one or more resins selected from the group consisting of (meth)acrylateresins and acrylonitrile-styrene resins, which have a weight averagemolecular weight, in terms of the polystyrene, of 400,000 or more, areused. In the present invention, the (meth)acrylate resin refers to bothor either of a methacrylate resin and an acrylate resin, unlessotherwise noted.

The (meth)acrylate resin used in the present invention is notparticularly limited, so long as it has a weight average molecularweight, in terms of the polystyrene, of 400,000 or more. Homopolymersand copolymers containing (30 to 100% by weight of a (meth)acrylatemonomer and 0 to 40% by weight of a monomer copolymerizable with the(meth)acrylate monomer (hereinafter referred to as “arbitrary monomer(2)”), the total content thereof being 100% by weight, are preferable.When the amount of the (meth)acrylate monomer is less than 60% byweight, the compatibility with the resin component (A) is reduced, andthe mechanical properties and the transparency may sometimes beinsufficient.

The ratio of the (meth)acrylate monomer and the arbitrary monomer (2) ispreferably a ratio of 70 to 100% by weight of the (meth)acrylate monomerand 0 to 30% by weight of the arbitrary monomer (2), more preferably aratio of 80 to 100% by weight of the (meth)acrylate monomer and 0 to 20%by weight of the arbitrary monomer (2), even more preferably a ratio of90 to 100% by weight of the (meth)acrylate monomer and 0 to 10% byweight of the arbitrary monomer (2).

The (meth)acrylate monomer may include, for example, methacrylateshaving an alkyl group with 1 to 22 carbon atoms such as methylmethacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, dodecylmethacrylate, stearyl methacrylate, and behenyl methacrylate; acrylateshaving an alkyl group with 1 to 22 carbon atoms and a hydroxyl groupsuch as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate;(meth)acrylates having an epoxy group such as glycidyl (meth)acrylate;and (meth)acrylates having an alkyl group with 1 to 22 carbon atoms andan alkoxy group. The number of carbon atoms of the alkyl group in the(meth)acrylate is not necessarily limited, but, for example, if thenumber of carbon atoms is more than 22, the polymerizability maysometimes be deteriorated, and thus it is possible to preferably use the(meth)acrylates having an alkyl group with 22 or less carbon atoms. The(meth)acrylates having an alkyl group with 1 to 12 carbon atoms are morepreferable, and the (meth)acrylates having an alkyl group with 1 to 8carbon atoms are even more preferable because they have the excellentcompatibility with the polyhydroxyalkanoate.

Known compounds can be used as the arbitrary monomer (2), and it ispreferable to use, for example, one or more compounds selected from thegroup consisting of vinyl arenes, vinylcarboxylic acids, vinyl cyanides,vinyl halides excluding vinyl chloride, vinyl acetate, alkenes, andalkynes.

The vinyl arenes may include styrene, α-methyl styrene,monochlorostyrene, dichlorostyrene, and the like. The vinylcarboxylicacids may include acrylic acid, methacrylic acid, itaconic acid, and thelike. The vinyl cyanides may include acrylonitrile, methacrylonitrile,and the like. The vinyl halides excluding vinyl chloride may includevinyl bromide, vinyl fluoride, and the like. The alkenes may includeethylene, propylene, butene, butadiene, isobutene, and the like. Thealkynes may include acetylene and the like. Of the arbitrary monomers(2), acrylonitrile and styrene are preferable in terms of thecompatibility with another resin and the like. The arbitrary monomer (2)may be used alone or as a mixture of two or more kinds.

The acrylonitrile-styrene resin used in the present invention is notparticularly limited so long as it has a weight average molecularweight, in terms of the polystyrene, of 400,000 or more. Homopolymersand copolymers which contains 60 to 100% by weight of a vinyl monomercontaining acrylonitrile and styrene, and 0 to 40% by weight of amonomer copolymerizable therewith (hereinafter referred to as “arbitrarymonomer (3)”), total amount thereof being 100% by weight, arepreferable. When the amount of the vinyl monomer is less than 60% byweight, the compatibility with the resin component (A) is reduced, andthe mechanical property and the transparency may sometimes beinsufficient.

The ratio of the vinyl monomer and the arbitrary monomer (3) ispreferably a ratio of 70 to 100% by weight of the vinyl monomer and 0 to30% by weight of the arbitrary monomer (3), more preferably a ratio of80 to 100% by weight of the vinyl monomer and 0 to 20% by weight of thearbitrary monomer (3), even more preferably a ratio of 90 to 100% byweight of the vinyl monomer and 0 to 10% by weight of the arbitrarymonomer (3).

The ratio of the acrylonitrile and the styrene in the vinyl monomer is,in terms of the compatibility with the resin component (A), preferably aratio of 5 to 40% by weight of the acrylonitrile and 60 to 95% by weightof the styrene, the total content of the acrylonitrile and the styrenebeing 100% by weight, more preferably a ratio of 10 to 35% by weight ofthe acrylonitrile and 65 to 90% by weight of the styrene, even morepreferably a ratio of 15 to 30% by weight of the acrylonitrile and 70 to85% by weight of the styrene, particularly preferably a ratio of 20 to30% by weight of the acrylonitrile and 70 to 80% by weight of thestyrene.

As the arbitrary monomer (3), any known monomer may be used. It ispreferable to use, for example, one or more monomers selected from thegroup consisting of (meth)acrylates, vinyl arenes, vinylcarbolic acids,vinyl halides excluding vinyl chloride, vinyl acetate, alkenes, andalkynes.

The (meth)acrylates may include, for example, methacrylates having analkyl group with 1 to 22 carbon atoms such as methyl methacrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl hexylmethacrylate, octyl methacrylate, dodecyl methacrylate, stearylmethacrylate, behenyl methacrylate; acrylates having an alkyl group with1 to 22 carbon atoms and a hydroxyl group such as 2-hydroxyethylacrylate, and 4-hydroxybutyl acrylate; (meth)acrylates having an epoxygroup such as glycidyl (meth)acrylate; (meth)acrylates having an alkylgroup with 1 to 22 carbon atoms and an alkoxy group, and the like. Thenumber of carbon atoms of the alkyl group in the (meth)acrylates are notnecessarily limited, but, for example, if the number of carbon atoms ismore than 22, the polymerizability may sometimes be deteriorated, andthus it is possible to preferably use the (meth)acrylates having analkyl group with 1 to 22 carbon atoms. In order to more improve thepolymerizability, it is more preferable to use (meth)acrylates having analkyl group with 1 to 12 carbon atoms, and (meth)acrylates having analkyl group with 1 to 8 carbon atoms are even more preferable, becausethey have the excellent compatibility with the polyhydroxyalkanoate.

The vinyl arenes may include α-methyl styrene, monochlorostyrene,dichlorostyrene, and the like. The vinylcarboxylic acids may includeacrylic acid, methacrylic acid, itaconic acid, and the like. The vinylhalides excluding vinyl chloride may include vinyl bromide, vinylfluoride, and the like. The alkenes may include ethylene, propylene,butene, butadiene, isobutene, and the like. The alkynes may includeacetylene and the like.

Of the arbitrary monomers (3), the (meth)acrylate are preferable interms of the compatibility with the resin component (A), and methylmethacrylate, butyl methacrylate, ethyl acrylate, and butyl acrylate aremore preferable. The arbitrary monomer (3) may be used alone or as amixture of two or more kinds.

The (meth)acrylate resin and the acrylonitrile-styrene resin have theexcellent compatibility, and thus these may be used together, or eitherone may be used.

The (meth)acrylate resin and the acrylonitrile-styrene resin, which isthe resin component (B), have a weight average molecular weight, in terof the polystyrene, of 400,000 or more, preferably 400,000 or more and10,000,000 or less.

When the weight average molecular weight, in terms of the polystyrene,is less than 400,000, the vinyl chloride resin cannot gel or thegelation of the vinyl chloride resin is insufficiently advanced, andthus it may sometimes be difficult to mold the resin composition. Inaddition, even if the resin composition can be molded, sufficientmechanical properties may not be exhibited. When the weight averagemolecular weight is more than 10,000,000, the resin component (B)remains in the molded article as a non-melted resin, and the moldedarticle may sometimes have a poor appearance. Even if the resincomponent (B) is melted, a poor appearance such as flow marks maysometimes be left.

The resin component (B) has a weight average molecular weight ofpreferably 700,000 or more and 6,000,000 or less, more preferably1,400,000 or more and 4,000,000 or less, in terms of the excellentability of gelling the vinyl chloride resin, in particular, in terms ofthe excellent releasability from a calendar roll upon the calendarmolding, and the reduced amount of the non-melted resin upon the moldingof the resin component (B), thus resulting in the reduced generation ofthe flow marks. The (meth)acrylate resin and the acrylonitrile-styreneresin, which is the resin component (B), have the excellentcompatibility with both the vinyl chloride resin and thepolyhydroxyalkanoate, and thus the transparency of the resin compositionof the invention is not reduced, or the reduction thereof can beminimized.

A method of measuring the weight average molecular weight of the(meth)acrylate resin or the acrylonitrile-styrene resin is notparticularly limited, and measurement methods utilizing a gel permeationchromatography (GPC) are preferable. One example of the measurementmethods is exemplified by a method in which tetrahydrofuran is used as amobile phase, a GPC system, manufactured by Tosoh Corporation (tradename: HLC-8220 GPC) is used as a system, and TSK guardcolumn Super HZ-Hand TSK gel Super HZM-H (trade name, a polystyrene gel), manufactured byTosoh Corporation, are used as a column filler. The weight averagemolecular weight can be obtained according to the method in terms of thepolystyrene. When it is difficult to dissolve the (meth)acrylate resinor the acrylonitrile-styrene resin in tetrahydrofuran, the solvent usedas the mobile phase can be appropriately changed.

The (meth)acrylate resin and the acrylonitrile-styrene resin have anumber average primary particle size of preferably 40 μm or less, morepreferably 1.5 μm or less, even more preferably 5 μm or less, furthereven more preferably 1 μm or less, particularly preferably 0.5 μm orless. When the number average primary particle size of the methacrylateresin and the acrylonitrile-styrene resin is more than 40 μm, the(meth)acrylate resin and/or the acrylonitrile-styrene resin may not bemelted by the composition of the resin composition of the invention ormelt-molding process of the present invention, and the non-melted resinremains in the molded article such as a sheet, thus resulting in thepoor appearance of the molded article.

The (meth)acrylate resin and the acrylonitrile-styrene resin, used inthe present invention, can be produced in a known method such as a bulkpolymerization, a melt polymerization, a solution polymerization,suspension polymerization, microsuspension polymerization, a dispersionpolymerization, or an emulsion polymerization. Of these polymerizationmethods of the resins, the suspension polymerization, themicrosuspension polymerization, the dispersion polymerization, and theemulsion polymerization are preferable, because resins having a numberaverage primary particle size of 40 μm or less can be easily produced.In order to make the number average primary particle size morepreferable, the microsuspension polymerization, the dispersionpolymerization, and the emulsion polymerization are more preferable, andthe emulsion polymerization is particularly preferable.

The primary particle size used herein refers to a particle size of theminimum unit particle, confirmed when the resin particles are directlyobserved with an electron microscope, or the like. Even when a part ofthe primary particles are fused to each other, each physical property ofthe resin composition of the invention is not affected. Recently, thereare unique polymerizations and production methods of fine particles, forexample, there are fine particles having a layered structure in which afine particle having a particle size of 1 μm is coated with a fineparticle having a particle size relatively larger than it, such as about150 μm. In such a case, the former size, 1 μm, is considered as theprimary particle size, and the particle size of the larger particles,about 150 μm, is considered as the secondary particle size. In thepresent invention, the number average primary particle size is obtainedby directly measuring particle sizes of 100 or more primary particlesusing the electron microscope and the like, and averaging the measuredvalues, as described above.

The (meth)acrylate resin and the acrylonitrile-styrene resin used in thepresent invention have a glass transition temperature Tg of preferably 0to 140° C., more preferably 30 to 120° C., even more preferably 40 to110° C., particularly preferably 45 to 95° C. When the glass transitiontemperature Tg is lower than 0° C., the vinyl chloride resin does notgel, or the gelation of the vinyl chloride resin may sometimes beinsufficiently advanced. When the glass transition temperature Tg of the(meth)acrylate resin or the acrylonitrile-styrene resin is higher than140° C., these resins remain in the molded article, such as a sheet,formed of the resin composition of the invention, as the non-meltedresin, and thus the molded article may sometimes have the poorappearance.

The glass transition temperature Tg of the (meth)acrylate resin and theacrylonitrile-styrene resin, used in the present invention, can bemeasured, for example, by a differential scanning calorie analysis or adynamic viscoelasticity measurement, but in the present invention theglass transition temperature Tg is a value calculated from a Fox formulausing values described in Polymer Hand Book (J. Brandrup, Interscience1989). For example, Tg of polymethyl methacrylate is 105° C., Tg ofpolybutyl acrylate is −54° C., and Tg of polymethacrylic acid is 228° C.

When Tg is measured according to the differential scanning calorieanalysis or the dynamic viscoelasticity measurement, as for at leastthree polymers (the vinyl chloride resin, the (meth)acrylate resin, andthe acrylonitrile-styrene resin), it is necessary to optimizemeasurement conditions so as to obtain values described in Polymer HandBook, because the Tg varies depending on the shape of a test sample tobe measured, the temperature-rising rate, and the like.

The blending amount of the resin component (B) in the resin compositionof the invention is from 0.1 to 8 parts by weight based on 100 parts byweight of the resin component (A), and it is preferably from 0.5 to 7parts by weight, more preferably 1 to 5 parts by weight, because boththe air marks and the flow marks can be suppressed, and the beautifulmolded article having the excellent transparency can be obtained. Whenthe blending amount of the resin component (B) is less than 0.1 parts byweight, unacceptable air marks may sometimes be generated. In addition,the gelation of the vinyl chloride resin cannot be sufficientlyadvanced, and the mechanical properties, the transparency, and the likemay sometimes not be expressed. When the blending amount of the resincomponent (B) is more than 8 parts by weight, the unacceptable flowmarks may sometimes be generated.

In the resin composition of the invention, the combinations of theblending amount of the vinyl chloride resin and thepolyhydroxyalkanoate, forming the resin component (A), and the blendingamount of the resin component (B) are as follows:

When 15 to 65 parts by weight of the vinyl chloride resin and 35 to 85parts by weight of the polyhydroxyalkanoate are blended as the resincomponent (A), the blending amount of the resin component (B) is from0.1 to 8 parts by weight, from 0.5 to 7 parts by weight, or from 1 to 5parts by weight. When “25 to 65 parts by weight of the vinyl chlorideresin and 35 to 75 parts by weight of the polyhydroxyalkanoate,” “35 to65 parts by weight of the vinyl chloride resin and 35 to 65 parts byweight of the polyhydroxyalkanoate,” “35 to 60 parts by weight of thevinyl chloride resin and 40 to 65 parts by weight of thepolyhydroxyalkanoate,” “40 to 60 parts by weight of the vinyl chlorideresin and 40 to 60 parts by weight of the polyhydroxyalkanoate,” or “40to 55 parts by weight of the vinyl chloride resin and 45 to 60 parts byweight of the polyhydroxyalkanoate” are blended as the resin component(A), the blending amount of the resin component (B) is from 0.1 to 8parts by weight, from 0.5 to 7 parts by weight, or 1 to 5 parts byweight.

<Plasticizer>

In the present invention, the vinyl chloride resin can be sufficientlysoftened by using the polyhydroxyalkanoate alone, but it is possible, ifnecessary, to use a plasticizer as an aid within a range in which theplasticizer migration of the resin composition of the invention is notincreased, whereby the resin composition is still more softened, and acold-resistance can be imparted to the resin composition. In order notto increase the plasticizer migration, the blending amount of theplasticizer is preferably 22 parts by weight or less, more preferably 18parts by weight or less, even more preferably 12 parts by weight orless, further even more preferably 7 parts by weight or less,particularly preferably 3 parts by weight or less, based on 100 parts byweight of the resin component (A).

As the plasticizer, which can be used in the present invention, knownplasticizers may be used, it may include, for example, phthalic acidester plasticizers such as di(n-butyl) phthalate, di(n-octyl) phthalate,di(2-ethylhexyl) phthalate, diisooctyl phthalate, octyldecyl phthalate,diisodecyl phthalate, butylbenzyl phthalate, anddi(2-ethylhexyl)isophthalate; phosphoric acid ester plasticizers such astributyl phosphate, tri(2-ethylhexyl) phosphate, (2-ethylhexyl) diphenylphosphate, and tricresyl phosphate; adipic acid ester plasticizers suchas di(2-ethylhexyl)adipate, diisodecyl adipate, (n-octyl) (n-decyl)adipate, and (n-heptyl) (n-nonyl) adipate; sebacic acid esterplasticizers such as dibutyl sebacate, di(2-ethylhexyl) sebacate,dioctyl sebacate, and diisooctyl sebacate; azelaic acid esterplasticizers such as di(2-ethylhexyl) azelate, dihexyl azelate, anddiisooctyl azelate; citric acid ester plasticizers such as triethylcitrate, triethyl acetylcitrate, tributyl citrate, tributylacetylcitrate, and tri(2-ethylhexyl) acetylcitrate; glycolic acid esterplasticizers such as methyl phthalyl ethylglycolate, ethyl phthalylethylglycolate, and butyl phthalyl butylglycolate; trimellitic acidester plasticizers such as tri(2-ethylhexyl) trimellitate, trioctyltrimellitate, di(n-octyl) mono(n-decyl) trimellitate, and diisooctylmonoisodecyl trimellitate; ricinoleic acid ester plasticizers such asmethyl acetyl ricinoleate, and butylacetyl ricinoleate; glycerolplasticizers such as glycerol diacetomonolaurate, glycerolmonoacetomonostearate, and medium chain fatty acid triglyceride; epoxyplasticizers such as epoxidized soybean oil, epoxidized linseed oil, andepoxidized (2-ethylhexyl)ester of tall oil fatty acid; polyesterplasticizers such as (1,3-butanediol) (2-ethylhexanol) adipatepolyester, (1,6-hexanediol) (2-ethylhexanol) sebacate polyester,(propyleneglycol) (coconut oil fatty acid) adipate polyester, and thelike,

As the present invention aims at providing the soft thermoplastic resincomposition having a small environmental load, it is preferable not touse the phthalic acid ester plasticizer, suspected of being anenvironmental hormone. The more preferable plasticizer are the polyesterplasticizers, which have the small plasticizer migration and bleedingout property, the trimellitic acid plasticizers such as trimellitic acidesters, the glycolic acid plasticizers such as glycolic acid esters, thecitric acid plasticizers such as citric acid esters, the glycerolplasticizers, the azelaic acid plasticizers such as azelaic acid esters,the sebacic acid plasticizers such as sebacic acid esters, and theadipic acid plasticizers such as adipic acid esters; the even morepreferable plasticizers are, in terms of the cold-resistance, thetrimellitic acid plasticizers, the glycolic acid plasticizers, theglycerol plasticizers, the azelaic acid ester plasticizers, the sebacicacid plasticizers, and the adipic acid plasticizers; still even morepreferably plasticizers are, in terms of the balance between theenvironmental load and the safety, the glycolic acid plasticizers andthe glycerol plasticizer; and the particularly preferable plasticizersare the glycerol plasticizers, because they have the excellentcompatibility with both of the vinyl chloride resin and thepolyhydroxyalkanoate. The plasticizer may be used alone or as a mixtureof two or more kinds.

The resin composition of the invention, which contains the plasticizer,contains 0.1 to 8 parts by weight of the resin component (B) and 22parts by weight or less of the plasticizer based on 100 parts by weightof the resin component (A). In the resin composition of the invention, ablending ratio of the vinyl chloride resin to the polyhydroxyalkanoate(parts by weight, the vinyl chloride resin/the polyhydroxyalkanoate) inthe resin component (A) may be set within a range of 15 to 65/35 to 85,25 to 65/35 to 75, 35 to 65/35 to 65, 35 to 60/40 to 65, 40 to 60/40 to60, or 40 to 55/45 to 60. The blending amount (parts by weight) of theresin component (B) may be within a range of 0.1 to 8, 0.5 to 7, or 1 to5. The blending amount (parts by weight) of the plasticizer may bewithin a range of 22 or less, 18 or less, 12 or less, 7 or less, or 3 orless.

<Stabilizer for Vinyl Chloride Resin>

The resin composition of the invention may contain a stabilizer for thevinyl chloride resin, within a range in which its excellent softness,transparency, and mold-processability are not impaired. The vinylchloride resin has a comparatively lower decomposition temperature, andthus it is preferable that the composition contains the stabilizer forthe vinyl chloride resin. As the stabilizer for the vinyl chlorideresin, a known stabilizer may be used. For example, it is possible touse one or more stabilizers for the vinyl chloride resin selected fromthe group consisting of metal soap stabilizers, lead salt stabilizers,metal liquid stabilizers, organotin stabilizers, and non-metalstabilizers.

The metal soap stabilizer is often used to attempt a synergistic effect,in which a larger effect can be obtained by using it together withanother one, rather than a case where it is used alone. Specificexamples thereof may include calcium stearate, barium stearate, zincstearate, and the like.

The lead salt stabilizer has a strong heat stability and an excellentweatherability. Specific examples thereof may include tribasic leadsulfate, dibasic lead phosphite, and the like.

The metal liquid stabilizer has a good compatibility with a resin or aplasticizer and has an effect of decreasing the softening temperature.It is, accordingly, characterized by suitably applying to softapplications. Specific examples thereof may include Ba/Zn stabilizers,Ca/Zn stabilizers, and the like.

The organotin stabilizer has the excellent heat resistance andweatherability, similar to the lead salt stabilizer, and it ischaracterized by having a large gelation promoting effect of the vinylchloride resin. Specific examples thereof may include laurate, maleate,mercapride (or mercapto) stabilizers.

The non-metal stabilizer is a compound having substantially no metal orhaving no metal at all, and it is an important existence when thestabilizer is assembled in lead removal. Specific examples thereof mayinclude epoxy compounds, phosphites, β-diketone compound, and the like.

The other stabilizer may include polyhydric alcohols such as sorbitol,trimethylol propane, pentaerithritol; N-containing compounds such asdiphenylthiourea, β-aminocrotonic acid esters, 2-phenyl indole, anddicyandiamide; hydrotalcites, and the like.

The resin composition of the invention are often applied to applicationrequiring the transparency, and thus it is preferable to use the metalliquid stabilizer or the organotin stabilizer, having the excellenttransparency. In addition, in order to increase the stability, anotherstabilizer may be suitably added.

It is preferable that the blending amount of the stabilizer is as smallas possible, in terms of the sanitation, and a minimum amount, which isnecessary for molding, of the stabilizer is used. Specifically, theamount thereof is preferably from 0.1 to 5 parts by weight, morepreferably from 0.1 to 4 parts by weight, even more preferably from 0.5to 4 parts by weight, still even more preferably from 1 to 4 parts byweight, particularly preferably from 1 to 3.5 parts by weight, based on100 parts by weight of the vinyl chloride resin. When the blendingamount of the stabilizer is less than 0.1 parts by weight based on 100parts by weight of the vinyl chloride resin, the heat stability maysometimes be insufficient, and when it is more than 5 parts by weight,sticking or plate-out may occur during molding, bleeding-out from themolded article may occur, the transparency may be insufficient, or aneluting amount is too large in an elution test.

The resin composition of the invention, which contains the stabilizerfor the vinyl chloride resin, contains 0.1 to 8 parts by weight of theresin component (B) and 0.1 to 5 parts by weight of the stabilizer forthe vinyl chloride resin based on 100 parts by weight of the resincomponent (A). The resin composition of the invention, which containsthe plasticizer and the stabilizer for the vinyl chloride resin,contains 0.1 to 8 parts by weight of the resin component (B) and 22parts by weight or less of the plasticizer based on 100 parts by weightof the resin component (A), and 0.1 to 5 parts by weight of thestabilizer for the vinyl chloride resin based on 100 parts by weight ofthe vinyl chloride resin.

In the two kinds of the resin compositions of the invention describedabove, a blending ratio of the vinyl chloride resin to thepolyhydroxyalkanoate (parts by weight, the vinyl chloride resin/thepolyhydroxyalkanoate) in the resin component (A) may be set within arange of 15 to 65/35 to 85, 25 to 65/35 to 75, 35 to 65/35 to 65, 35 to60/40 to 65, 40 to 60/40 to 60, or 40 to 55/45 to 60. The blendingamount (parts by weight) of resin component (B) may be within a range of0.1 to 8, 0.5 to 7, or 1 to 5. The blending amount (parts by weight) ofthe plasticizer may be within a range of 22 or less, 18 or less, 12 orless, 7 or less, or 3 or less. The blending amount (parts by weight) ofthe stabilizer for the vinyl chloride resin may be within a range of 0.1to 5, 0.1 to 4, 0.5 to 4, 1 to 4, or 1 to 3.5.

<Other Compounding Agent, Thermoplastic Resin, and Elastomer, which canbe Added>

To the resin composition of the invention may be added, if necessary,one or more components selected from the group consisting of knowncompounding agents, thermoplastic resins other than the resin component(A) and the resin component (B), and elastomers within a range in whichthe effects of the present invention are not impaired.

(Compounding Agent)

As the compounding agent, compounding agents which are usually added toa resin composition may be used without any limitation, and examplesthereof may include fillers, reinforcements, anti-oxidants, ultravioletabsorbents, flame retardants, anti-static agents, lubricants,stabilizers, coloring agents, fungicidal microbicide, surface-treatingagents, ant repelling agents, repellents for mice, reodorants, releasingagents, fluidity improving agents, compatibilizers, melt-viscositycontrolling agents, light diffusing agents, antifouling agent,antifogging agents, nucleating agents, infrared absorbents, and thelike.

Any known filler and reinforcing agent may be used, and examples thereofmay include powdery fillers such as calcium carbonate, silica, and clay;flat plate fillers such as mica, talc, kaolin clay, graphite, andselenite; needle-shaped fillers such as asbestos, wollastonite,sepiolite, phosphate fiber, gypsum fiber, and MOS; spherical fillerssuch as shirasu balloon, glass balloon, and carbon balloon; fiberfillers such as linter, glass fibers, aramid fibers, carbon fibers, andnatural fibers; other fillers such as tetrapod-shaped zinc oxide. Thediameter of the powdery, spherical, needle-like, or fiber fillers andthe thickness of the at plate fillers are preferably 10 μm or less, morepreferably 3 μm or less, even more preferably 1 μm or less, particularlypreferably 0.3 μm or less, because of the excellent transparency.

Any known antioxidant may be used, and examples thereof may includephenol antioxidants exemplified by 2,6-di-tert-butyl-para-cresol; amineantioxidants exemplified by phenyl-β-naphthylamine; sulfur antioxidantsexemplified by lauryl stearyl thiodipropionate; phosphorus antioxidantsexemplified by tridecyl phosphite; hydrazine antioxidants exemplified byN-salicyloyl-N′-aldehydehydrazine; amide antioxidants exemplified byN,N′-diphenyl oxide; acid antioxidants exemplified by phosphoric acidand citric acid, and the like.

Any known ultraviolet absorbent may be used, and examples thereof mayinclude benzophenone ultraviolet absorbents, salicylate (benzoate)ultraviolet absorbents, benzotriazole ultraviolet absorbents, andcyanoacrylate ultraviolet absorbents. In addition, it may also includemetal complex salts, which are used as a quencher, and hinderedpiperidine, which is used as a hindered amine light stabilizer (HALS).

Any known flame retardant may be used, and examples thereof may includehalogen flame retardants exemplified by tetrabromobisphenol A andbrominated polystyrene; phosphorus flame retardants, which improve theflame retardance by using it together with the halogen flame retardant,exemplified by antimony trioxide, triphenyl phosphate, tricresylphosphate, and resorcinol bis(diphenylphosphate); and inorganic flameretardants exemplified by aluminum trihydroxide and magnesiumdihydroxide. It is preferable to use the phosphorus flame retardant,because it has the excellent compatibility with the resin component (A),and shows a softening effect.

Any known anti-static agent may be used, and examples thereof mayinclude cationic active agent-type anti-static agents exemplified byprimary amine salts, tertiary amine, and quaternary ammonium compounds;anionic active agent-type anti-static agents exemplified by sulfonatedoil, soap, alkyl sulfate salts, alkyl benzene sulfonates, phosphatesalts; nonionic active agent-type anti-static agents exemplified bypartially fatty acid esters of polyhydric alcohol, ethylene oxide adductof aliphatic alcohol, and ethylene oxide adducts of alkyl naphthol; andamphoteric active agent-type anti-static agents exemplified bycarboxylic acid derivatives and imidazoline derivatives. Similarly,various polymer-type anti-static agents may be used.

Any known lubricant may be used, and examples thereof may includehydrocarbon lubricants exemplified by paraffin and polyethylene wax;aliphatic acid lubricants exemplified by higher fatty acids and hydroxyfatty acids; fatty acid amide lubricants exemplified by fatty acid amideand alkylene bisfattyacid amide; ester lubricants exemplified by loweralcohol esters of fatty acid and polyglycol ester; alcohol lubricantsexemplified by aliphatic alcohols and polyglycol; polymer lubricantsexemplified by various metal soaps and silicone, and the like.

Any known nucleating agent may be used, and examples thereof may includehigher fatty acid amide, urea derivatives, sorbitol compounds, boronnitride, higher fatty acid salts, aromatic fatty acid salts, and thelike. Of these, the higher fatty acid amide, the urea derivative, andthe sorbitol compound are preferable, because of the high effect as thenucleating agent.

Each of the compounding agents described above may be used alone or as amixture of two or more kinds.

(Thermoplastic Resin other than Resin Component (A) and Resin Component(B))

The thermoplastic resin other than the resin component (A) and the resincomponent (B), which can be preferably used in the present invention,may include, for example, polyester resins; polycarbonate resins;polyamide resins; polyacetal resins; polyvinyl acetal resins; polyketoneresins; polyolefin resins; and vinyl polymer or copolymer resinsobtained by polymerization or copolymerization of one or more vinylmonomers selected from the group consisting of diene compounds,maleimide compounds, aromatic alkenyl compounds, methacrylic acidesters, acrylic acid esters, and vinyl cyanide compounds. They may beused alone or as a mixture of two or more kinds.

The polyester resin may be exemplified by resins obtained bypolycondensation of a dicarboxylic acid or a derivative thereof such asan alkyl ester with a diol; resin obtained by polycondensation of amonomer having both of a carboxylic acid or a derivative thereof such asan alkyl ester, and a hydroxyl group in one molecule; and resinsobtained by ring-opening polymerization of a monomer having a cyclicester structure in one molecule. The term polyester resin here is theresin other than the polyhydroxyalkanoate which is used as the resincomponent (A).

The dicarboxylic acid forming the polyester resin may includeterephthalic acid, isophthalic acid, naphthalene dicarboxylic acid,succinic acid, adipic acid, sebacic acid, and the like. The dial mayinclude ethane dial, propane diol, butane diol, pentane diol, neopentylglycol, hexane diol, cyclohexane dimethanol, and the like. The monomerhaving both of a carboxylic acid or a derivative thereof such as analkyl ester and a hydroxyl group in one molecule may include lactic acidand the like. The monomer having a cyclic ester structure in onemolecule may include caprolactone and the like.

Specific examples of the polyester resin may include polymethyleneterephthalate, polyethylene terephthalate, polypropylene terephthalate,polytetramethylene terephthalate, polybutylene terephthalate,polyhexamethylene terephthalate, polycyclohexanedimethyleneterephthalate (which hereinafter may sometimes be referred to as PCT),poly(ethylenecyclohexenedimethylene)terephthalate, glycol modifiedpolyethylene terephthalate (which hereinafter may sometimes be referredto as PETG), polyethylene naphthalate, polytrimethylene naphthalate,polybutylene naphthalate, polycyclohexanedimethylene naphthalate,polyarylate, polylactic acid, polysuccinic acid ethylene, polysuccinicacid butylene, polyadipic acid butylene, poly-ε-caprolactone,poly(α-oxyacid), and copolymers thereof. In the present invention. PETG,polylactic acid, polysuccinic acid ethylene, polysuccinic acid butylene,polyadipic acid butylene, poly-ε-caprolactone, and poly(α-oxyacid) areparticularly preferable, because they have the excellent compatibilitywith the resin component (A). They may be copolymer thereof.

The polycarbonate resin is obtained by reaction of a dihydric phenolwith phosgene or a carbonate precursor, and may include aromaticpolycarbonate resins, and aliphatic polycarbonate resins. Any of themmay be used, and the aliphatic polycarbonate resins are preferable interms of the compatibility with the resin component (A) and thedecomposition temperature. In addition, copolymers with apolyamide-polycarbonate resin, a polyester-polycarbonate resin, or thelike may be used.

The polyamide resin may include polyamides obtained from an aliphatic,alicyclic, or aromatic diamine and an aliphatic, alicyclic, or aromaticdicarboxylic acid, polyamides obtained by a ring-opening polymerizationof a lactam such as ε-caprolactam or ω-dodecalactam, or polyamidesobtained from 6-aminocaproic acid, 1,1-aminoundecanoic acid,1,2-aminododecanoic acid, or the like in which the polyamides may behornopolymers, copolymers of the polyamide, and blends thereof. Thealiphatic polyamide resins are preferable in terms of the compatibilitywith the resin component (A) and the decomposition temperature. Ofthese, nylon-6, nylon-6,6, nylon-11, nylon-12, nylon-6,10, nylon-4,6,copolymers thereof, and blends thereof, which are industrially producedat a low cost and in a large amount, are more preferable. From the sameviewpoint, nylon-11 and nylon-12 are even more preferable.

The polyacetal resin refers to a polyoxymethylene, which includeshomopolymer-type resins, copolymer-type resins, and block-polymer-typeresins. A copolymerizable component in the copolymer and block-polymermay include oxyethylene, oxytrimethylene, oxytetramethylene, and thelike. The copolymer-type resin is preferable in terms of thecompatibility with the resin component (A) and the decompositiontemperature.

The polyvinyl acetal resin refers to a polyvinyl alcohol modified withan aldehyde, and may include polyvinyl formal, polyvinyl butyral, andthe like.

The polyketone resin may include aromatic polyketones, alicyclicpolyketones, aliphatic polyketones. The aliphatic polyketone ispreferable in terms of the compatibility with the resin component (A)and the decomposition temperature. Examples of the aliphatic polyketonemay include alternating copolymers of ethylene and carbon monooxide,alternating copolymers of an α-olefin and carbon monooxide, and thelike.

The polyolefin resin may include not only polymers from an olefin aloneexemplified by polyethylene, polypropylene, polymethylpentene,polybutene, cycloolefinpolymer, and copolymers thereof, but alsocopolymers of an olefin and copolymerizable compound having at least onedouble bond copolymerizable with the olefin. The copolymerizablecompound may include (meth)acrylic acid and its esters, maleic acid andits esters, maleic anhydride, vinyl acetate; vinyl chloride, carbonmonooxide, and the like. It is preferable to use the copolymerizablecompound in a ratio of 40% by weight or less.

There are several methods to disperse the polyolefin resin in the resincomponent (A). The polyolefin resin is divided into a non-reactive typeand a reactive type, in which the non-reactive type is a type which isreacted neither with the vinyl chloride resin nor thepolyhydroxyalkanoate, and the reactive type is a type which is reactedeither or both with the vinyl chloride resin and thepolyhydroxyalkanoate.

The non-reactive type may specifically include ethylene-vinyl acetatecopolymers, ethylene-vinyl acetate-carbon monooxide copolymers,ethylene-acrylic acid ester-carbon monooxide copolymers, ethylene-vinylchloride copolymers, and the like. They have the good compatibility withthe resin component (A), and thus they can easily form alloy with theresin component (A) only by melt-kneading.

The reactive type may specifically include non-reactive type polyolefinresin with which a monomer having a reactive functional group iscopolymerized, mainly in a case of the reaction with thepolyhydroxyalkanoate, and typical reactivity functional groups mayinclude an epoxy group, an acid group for oxo group), a hydroxyl group,an isocyanate group, and the like. The reaction may be performed at anappropriate processing temperature using, if necessary, a reactionblocking agent or a reaction accelerator. Another approach in thereactive type may include a dynamically cross-linking method. Thereaction with the polyhydroxyalkanoate can be performed using a radicalgenerator capable of effectively generating radicals at a processingtemperature. The radical generator is mainly reacted with thepolyhydroxyalkanoate, and forms a covalent bond between thepolyhydroxyalkanoate and the reactive type, whereby it functions as acompatibilizer, thus resulting in obtaining the alloyed product.

The other vinyl resin may include polymer and copolymer resins obtainedby polymerization or copolymerization of one or more monomers selectedfrom the group consisting of diene compounds, maleimide compounds,aromatic alkenyl compounds, methacrylate, acrylate, and vinyl cyanidecompound.

The polymer and the copolymer resin may include polystyrene resins,s-polystyrene resins, poly methyl methacrylate resins, polychlorostyreneresins, polybromostyrene resins, poly-α-methyl styrene resins,styrene-acrylonitrile copolymer resins, styrene-methyl methacrylatecopolymer resins, styrene-maleic anhydride copolymer resins,styrene-maleimide copolymer resins, styrene-N-phenyl maleimide copolymerresins, styrene-N-phenyl maleimide-acrylonitrile copolymer resins,methyl methacrylate-butyl acrylate copolymer resins, methylmethacrylate-ethyl acrylate copolymer resins,styrene-acrylonitrile-α-methyl styrene terpolymer resins,butadiene-styrene copolymer (HIPS) resins, acrylonitrile-butadienerubber-styrene copolymer (ABS)resins, acrylonitrile-acrylicrubber-styrene copolymer (ASA), acrylonitrile-ethylene propylenerubber-styrene copolymers, acrylonitrile-ethylene propylene dienerubber-styrene copolymers, acrylonitrile-butadiene rubber-α-methylstyrene copolymer resins, aromatic alkenyl compound-diene-vinylcyanide-N-phenyl maleimide copolymer resins, and the like.

Of the other vinyl resins described above, the polymethyl methacrylateresins, styrene-acrylonitrile copolymer resins, acrylonitrile-butadienerubber-styrene copolymer (ABS) resins, acrylonitrile-acrylicrubber-styrene copolymers (ASA), acrylonitrile-ethylene propylenerubber-styrene copolymers, and acrylonitrile-ethylene propylene dienerubber-styrene copolymers are preferable in terms of the compatibilitywith the resin component (A) and the decomposition temperature.

However, in the present invention, the composition containing either orboth of the (meth)acrylate resin and the acrylonitrile styrene resinhaving a weight average molecular weight, in terms of the polystyrene,of 400,000 or more, which is used as the resin component (B), isexcluded. In addition, the processable upper limit temperature, whenconsidering the decomposition temperature of the vinyl chloride resin,is about 220° C., and the processable upper limit temperature, whenconsidering the decomposition temperature of the polyhydroxyalkanoate,is about 240° C.

The blending amount of the thermoplastic resin is preferably 40 parts byweight or less, more preferably 30 parts by weight or less, even morepreferably 20 parts by weight or less, particularly preferably 10 partsby weight or less, based on 100 parts by weight of the resin component(A). These thermoplastic resin are secondarily used in order to keep thequality balance of the resin composition of the invention, and when theblending amount of the thermoplastic resin is more than 40 parts byweight, the softness and mechanical properties of the resin compositionof the invention may sometimes be reduced.

(Elastomer)

Any natural rubber or synthetic rubber may be used without anylimitation as the elastomer. The synthetic rubber may include, forexample, acrylic rubber such as butyl acrylate rubber, ethyl acrylaterubber, and octyl acrylate rubber; nitrile rubber such as abutadiene-acrylonitrile copolymer; chloroprene rubber, butadiene rubber,isoprene rubber, isobutylene rubber, styrene-butadiene rubber, methylmethacrylate-butyl acrylate block-copolymers, styrene-isobutyleneblock-copolymers, styrene-butadiene block-copolymers, hydrogenatedstyrene-butadiene block-copolymers, ethylene-propylene copolymers (EPR),hydrogenated ethylene-butadiene copolymers (EPDM), ethylene-vinylacetate copolymers, ethylene-vinyl acetate-carbon monooxide copolymers,polyurethane, chlorosulfonated polyethylene, silicone rubber (millabletype and room temperature vulcanizable type), butyl rubber,fluororubber, olefin thermoplastic elastomer, styrene thermoplasticelastomer, urethane thermoplastic elastomer, polyamide thermoplasticelastomer, polyester thermoplastic elastomer, fluorine-containingthermoplastic elastomer, and the like.

Rubber having a multiple bond in its structure can form an alloystructure capable of expressing the sufficient quality due to thedynamical cross-linking, even if the compatibility with the resincomponent (A) is low.

In the elastomer described above, the methyl methacrylate-butyl acrylateblock-copolymer, ethylene-vinyl acetate copolymer, ethylene-vinylacetate-carbon monooxide copolymer, and urethane thermoplastic elastomerare preferable, and the ethylene-vinyl acetate-carbon monooxidecopolymer is particularly preferable, because of the excellentcompatibility with the resin component (A).

<Compounding and Molding>

In the present invention, the vinyl chloride resin and thepolyhydroxyalkanoate as the resin component (A); at least one resinselected from the group consisting of (meth)acrylate resins andacrylonitrile styrene resins having a weight average molecular weight,in terms of the polystyrene, of 400,000 or more as the resin component(B); and, if necessary, at least one member selected from the groupconsisting of the plasticizer, the stabilizer for the vinyl chlorideresin, the compounding agent, the thermoplastic resin other than theresin component (A) and the resin component (B), and the elastomer areused as the starting materials, and the starting materials arecompounded in a known method, whereby the resin composition of theinvention can be obtained, and further the obtained resin composition ofthe invention can be molded in a known method.

As for the compounding, the compound may be a non-melted compoundobtained just by mixing the starting materials described above, withoutmelting them, or may be a granular compound, which has a shape capableof being easily molded, obtained by compressing or sticking thenon-melted compound, or completely melting the non-melted compound. Inany case, the starting materials may be added at once, or added instages in mid-course. In particular, when the starting materials aredifferent shapes to each other, for example, pellets, a powder, andliquid, it is preferable to add them by using multiple feeders.

Any known method may be utilized for preparing the non-melted compound,and examples thereof may include methods using a mixer such as aHenschel mixer or a tumbler. Any known method may also be utilized forpreparing the granular compound, and examples thereof may includemethods using a kneader such as a roll compaction machine, a gearpelletizer, Banbury mixer, or various extruders.

In order to show the mold-processability and the qualities (themechanical properties, the softness, the transparency, the lowplasticizer migration, and the like) of the resin composition of theinvention by sufficiently expressing the performances of the vinylchloride resin, to a maximal degree, it is necessary to apply heat andshear to the vinyl chloride resin, whereby the vinyl chloride resin issufficiently gelled. When a whole amount of the polyhydroxyalkanoate isadded before the vinyl chloride resin is sufficiently melt-kneaded, themelt-viscosity of the mixture is reduced, the shear is not applied tothe vinyl chloride resin, and the gelation is not sufficiently advanced,thus resulting in the reduction of the mechanical properties and thetransparency of the obtained molded article. It is preferable,accordingly, that the vinyl chloride resin is sufficiently gelled by anappropriate melt-kneading method.

As the appropriate melt-kneading method described above may preferablyinclude, for example, a first melt-kneading method in which after thevinyl chloride resin is melt-kneaded, the polyhydroxyalkanoate isafter-added, and they are melt-kneaded; a second melt-kneading method inwhich after the vinyl chloride resin and a part of thepolyhydroxyalkanoate are mixed and melt-knead, the remainder of thepolyhydroxyalkanoate is added to the obtained kneaded product at once orin batches, and the mixture is melt-kneaded; a third melt-kneadingmethod in which the whole amount of the vinyl chloride resin is mixedand melt-kneaded, or the whole amount of the vinyl chloride resin and apart of the polyhydroxyalkanoate are mixed and melt-kneaded to form asolid compound (for example, pellets), and the solid compound is mixedwith the whole amount of the polyhydroxyalkanoate or the remainderthereof and the mixture is melt-kneaded, and the like.

Specific examples of the second melt-kneading method may include amethod containing a pre-kneading step of melt-kneading the vinyl,chloride resin and a part of the polyhydroxyalkanoate; and amain-kneading step of adding the remainder of the polyhydroxyalkanoateto the kneaded product obtained in the pre-kneading step once or inbatches while, if necessary, the kneaded product is molded and the shapethereof is kept, and then melt-kneading the mixture. At that time, akneaded product obtained in the pre-kneading step is compounded, and theobtained compound is melted and may be used in the main-kneading step asa kneaded product obtained in the pre-kneading step. Alternatively, thekneaded product obtained in the main-kneading step may be compounded andmolded in a molding method described below. When a homopolymer having adegree of polymerization of 750 to 1200 or 900 to 1200 is used as thevinyl chloride resin, and the amount of the polyhydroxyalkanoate addedin the pre-kneading step is set at 5 to 90% by weight, 10 to 80% byweight, or 12 to 75% by weight, of the total blending amount, both ofthe moldability and the physical properties of the obtained moldedarticle can be obtained at a very high level.

The melt-kneading methods described above are preferable, because bothof the sufficient gelation of the vinyl chloride resin and thecompatibility of the vinyl chloride resin with the polyhydroxyalkanoatecan be realized at a high level by the melt-kneading methods, and themolded article can be obtained which has the excellent transparency,softness, and mechanical properties, and has the remarkably reducedplasticizer migration. The second melt-kneading method is morepreferable among the methods described above, because it furtherimproves the moldability of the resin composition of the invention orthe physical properties of the obtained molded article.

It is preferable that the vinyl chloride resin and thepolyhydroxyalkanoate, used in the kneading method described above, areseparately compounded. The compound of the vinyl chloride resin mayinclude, in addition to the vinyl chloride resin, a part of the resincomponent (B), the stabilizer for the vinyl chloride resin, theplasticizer, the lubricant, and the like. In addition, the compound ofthe polyhydroxyalkanoate may include, in addition to thepolyhydroxyalkanoate, the remainder of the resin component (B), theplasticizer, the lubricant, and the like.

In the compound of the vinyl chloride resin, the plasticizer is added,for example, to further promote the gelation of the vinyl chlorideresin. It is preferable that the plasticizer is added, before the vinylchloride resin is melted, to the vinyl chloride resin in an amount ofpreferably 60% by weight or more, more preferably 70% by weight or more,even more preferably 80% by weight or more, still even more preferably90% by weight or more, particularly preferably 100% by weight, of thewhole amount of the plasticizer.

The resin component (B) not only promotes the gelation of the vinylchloride resin, as with the plasticizer, but also has a function as amelt-viscosity regulator. In order to effectively and uniformly melt-mixtwo or more resins as much as possible, it is preferable that thedifference in the melt-viscosity is as small as possible in the two ormore resins, as derived from Wu's formula (S. Wu, J. Polym. Sci., C34,19 (1971)). From this viewpoint, it is preferable that the resincomponent (B) is contained in the compound of the vinyl chloride resinor the polyhydroxyalkanoate, as described above, or it is appropriatelydivided into several portions, and added to the melt-kneaded product ofthe vinyl chloride resin and the polyhydroxyalkanoate in batches.

The thus obtained resin composition of the invention is molded, wherebythe molded article of the present invention, which has the excellenttransparency, softness, and mechanical properties, and the remarkablyreduced plasticizer migration, can be obtained.

Examples of the molding method may include injection methods (insertmolding, two-color molding, sandwich molding, gas injection molding, andthe like), extrusion molding methods, inflation molding methods, T-diefilm forming methods, lamination molding methods, blow-molding ethods,hollow molding methods, compression molding methods, calendar moldingmethods, rotational molding methods, transfer molding methods, vacuummolding methods, powder slush molding methods, cast molding methods, andthe like.

In the resin composition of the invention, the melt-viscosity can bewidely controlled and it can be applied to various molding methods bychanging the blending amount or the weight average molecular weight ofthe resin component (B), containing the plasticizer or not, or changingthe blending amount of the plasticizer when it is added, as describedabove. Considering the melt-viscosity range in a composition capable ofeasily expressing the quality, it is preferable to use the injectionmolding method, the extrusion molding method, the inflation moldingmethod, the T-die film forming method, the blow-molding method, thecalendar molding method, or the vacuum molding method. The injectionmolding method, the extrusion molding method, the T-die film formingmethod, and the calendar molding method are more preferable, theextrusion molding method and the calendar molding method are even morepreferable, and the calendar molding method is particularly preferable.

Next, the calendar molding method is shown as one example of the moldingmethods of the resin composition of the invention. The calendar moldingmethod is a molding method containing a roll forming step and a coolingstep as essential steps, and if necessary, a pre-kneading step performedbefore the roll forming step, a press-forming step performed after theroll forming step, and the like. In the roll forming step, one or morekneading molding machines comprising two or more rolls having a heatertherein are used. Typical kneading molding machines may include, forexample, mixing roll formed of two rolls, warming roll formed of tworolls, and the like. If necessary, after the rolls, a calendar rollformed of 4 to 9 rolls may be installed.

In the roll forming step, the resin component (A), the resin component(B), and the other starting materials such as the compounding agent aresupplied to the surface of the rolls which are heated to apre-determined temperature and are rotated, whereby the startingmaterials are melt-kneaded and the obtained kneaded product is formedinto a sheet. Here, the temperature of the roll surface is suitablyselected depending on the kind of the starting material, the blendingamount, and the like, and it is selected from a range of generally 150to 200° C., preferably 155° C. to 195° C., more preferably 160 to 190°C. As the resin component (A) supplied to the roll surface, a compoundin which a part of the resin component (B) and the lubricant are addedto the vinyl chloride resin; a compound in which all or a part of thepolyhydroxyalkanoate, all or a part of the resin component (B),lubricant, and the like are added to the vinyl chloride resin by thesecond melt-kneading method; and a compound in a pellet state, obtainedby the third melt-kneading method are preferable.

In the pre-kneading step performed before the roll forming step ifnecessary, as the kneader, for example, a batch type Banbury mixer, aplanetary extruder, a single-screw extruder, a twin-screw extruder, orthe like are used. In this step, the starting materials are compounded,or the starting materials and the compounds thereof and the like arepreviously melted. When the pre-kneading step is performed, theproductivity of the calendar molding can be increased.

In the press-forming step performed after the roll forming step ifnecessary, both ends in the width direction of the sheet-like moldedarticle, obtained in the roll forming step, is cut according to thedemand using a press-forming machine containing a heating press and acooling press disposed on the downstream side of the heating press, theobtained sheets are joined on top of each other, the overlapped sheetsare put in a heating press to pre-heat and pressure-heat the sheets,and, immediately after, the sheets are put in a cooling press to coolthem, whereby a sheet-like molded article formed of the resincomposition of the invention and having a pre-determined thickness canbe obtained. The heating temperature of the heating press on thepressure-heat is suitably selected depending on the composition of theresin composition of the invention forming the sheet-like moldedarticle, and it is selected from a temperature range of preferably about−20° C. to +20° C. higher, more preferably about −10° C. to +10° C.higher than the surface temperature of the roll (a melt-kneadingtemperature) in the roll forming step. The press pressure of the heatingpress and the cooling press is not particularly limited, and it isappropriately selected depending on the composition of the resincomposition of the invention forming the sheet-like molded article, thedesign thickness of the sheet-like molded article, or the like.

The preferable embodiments of the method for producing the moldedarticle comprising the resin composition of the invention may include,for example, a method comprising a pre-kneading step of melt-kneadingthe vinyl chloride resin and a part of the polyhydroxyalkanoate; a mainkneading step of adding the remainder of the polyhydroxyalkanoate to thekneaded product obtained in the pre-kneading step once or in batches,while the shape of the kneaded product is regulated if necessary, andmelt-kneading the mixture; and a forming step of forming the kneadedproduct obtained in the main kneading step or the kneaded product havinga pre-determined shape into a molded article having a desired shape.When the calendar molding method is utilized in this production method,for example, in the pre-kneading step of the calendar molding, the mainkneading step, or the pre-kneading step and the main kneading step ofthe production method may be performed, and in the roll forming step andpress-forming step, the forming step of the production method may beperformed.

EXAMPLE

The present invention is explained in more detail on the basis ofExamples, but the present invention is not limited to only Example. Inthe present Examples, “parts” and “%” shows “parts by weight” and “% byweight”, respectively, unless otherwise noted. A measurement method ofeach physical properties is as follows:

(1) Method of Measuring HAZE

An HAZE of a sheet-like molded article having a thickness of LO mm,obtained by a press-forming described below, was measured using a hazemeter (manufactured by Nippon Denshoku Industries Co., Ltd., a model:NDH 2000) in accordance with JIS K 7136.

(2) Tensile Testing Method

A tensile breaking stress, a tensile break elongation, and a tensileelasticity of a sheet-like molded article having a thickness of 1.0 mm,obtained by the press-forming, was measured in accordance with JIS K6251. The shape of a test piece was a No. 2 dumbbell piece, and a testspeed was 500 mm/minute.

(3) Plasticizer Migration Testing Method

A sheet-like molded article having a thickness of 1.0 mm, obtained bythe press-forming, was put between black PMMA plates, to which apressure of 1 MPa was applied, and it was kept in a thermostatic chamberhaving a temperature of 80° C. for 6 hours. After that, the moldedarticle was peeled off from the black PMMA plates, and the black plateswere classified into 1 to 4 ranks based on a degree of whitening of theblack PMMA plate and the relative comparison was performed. Rank 4 isthe best in which the plate is hardly whitened, and Rank 1 is the worstin which the plate is white due to the very high plasticizer migration.If the plate is in Rank 3 or more, the plate has no problem in theplasticizer migration.

(4) Evaluation Method of Air Mark and Flow Mark

A sheet-like molded article obtained by the roll-forming was visuallyobserved, and the evaluation was performed according to the followingcriteria. The air mark refers to a molding failure of air bubbleremaining in a sheet-like molded article, generated by a phenomenon inwhich air, caught in kneading, cannot go through between rollers when itis passed through them; and the flow mark refers to a molding failure offlow patterns remaining on the sheet-like molded article, caused by aphenomenon in which a resin rich area (also referred to as “roll bank”)generated between the rolls is still left even after the resin is passedthrough between the rolls without relaxation.

<Evaluation Criteria of Air Mark>

⊚: No air marks are observed, and the appearance is beautiful with ahigh texture.∘: No air marks are observed, and the appearance is sufficient as amolded article of a general soft resin.Δ: Air marks are observed by a careful observation, but the appearanceis acceptable for practical use as a molded article of a general softresin.x: Air marks are observed, fine irregularities exist partly on thesurface, and the appearance is poor.

<Evaluation Criteria of Flow Mark>

∘: No flow marks are observed, and the appearance is beautiful with ahigh texture.∘: No flow marks are observed, and the appearance is sufficient as amolded article of a general soft resin.Δ: Flow marks are observed by a careful observation, but the appearanceis acceptable for practical use as a molded article of a general softresin,x: Flow marks are observed, fine irregularities exist partly on thesurface, and the appearance is poor.

(5) Evaluation Method of Particle

The particle used here refers to a non-melted resin, which can beconfirmed by visually observing the sheet-like molded article. Theevaluation was performed by a two-stage evaluation in which ◯ (there isa non-melted resin in an amount so that there are no problems inpractical use) and x (a non-melted resin can be easily visuallyobserved, and there are problems in practical use).

Synthetic Example 1 Synthesis of PHA-2

As a polyester producing strain, KNK-631 strains (see WO2009/145164)were used. Culture was performed as follows: A composition of a motherseed medium was: meat extract: 1 w/v %, Bacto (trademark)-Tryptone(casein triptone, manufactured by Difco Inc.): 1 w/v %, yeast extract:0.2 w/v %, Na₂PO₄.12H₂O: 0.9 w/v %, 0.15 w/v % (pH 6.8), and kanamycinsulfate: 5×10⁻⁶ w/v %.

A composition of a preculture medium was: Na₂PO₄.12H₂O: 1.1 w/v %,KH₂PO₄: 0.19 w/v %, (NH₄)₂SO₄: 1.29 w/v %, MgSO₄.7H₂O: 0.1 w/v %, palmkernel oil olefin: 2.5 w/v %, a solution containing slight, amount ofmetal salts (FeCl₃.6H₂O: 1.6 w/v %, CaCl₂.2H₂O: 1 w/v %, CoCl₂.6H₂O:0.02 w/v %, CuSO₄.5H₂O: 0.016 w/v %, and NiCl₂.6H₂O: 0.012 w/v % weredissolved in 0.1 N hydrochloric acid): 0.5 v/v %.

A composition of a polyester production medium was Na₂PO₄.12H₂O: 0.385w/v %, KH₂PO₄: 0.067 w/v %, (NH₄)₂SO₄: 0.291 w/v %, MgSO₄.7H₂O: 0.1 w/v%, a solution containing slight amount of metal salts (FeCl₃.6H₂O: 1.6w/v %, CaCl₂.2H₂O: 1 w/v %, CoCl₂.6H₂O: 0.02 w/v %, CuSO₄.5H₂O: 0.016w/v %, and NiCl₂.6H₂O: 0.012 w/v % were dissolved in 0.1 N hydrochloricacid): 0.5 v/v %, an antifoaming agent (trade name: BIOSPUMEX 200K,manufactured by Cognis Japan Ltd.): 0.05 w/v %. As a carbon source, palmkernel oil olein, which was a low melting point fraction obtained byfractionating palm kernel oil, was used. As an aqueous phosphatesolution for pouring, a solution having 4.00 w/v % of Na₂HPO₄.12H₂O and0.69 w/v % of KH₂PO₄ was used.

Glycerol stock (50 μl) containing KINK-631 strains was seeded in themother seed medium (10 ml), which was cultured for 24 hours, and theresulting product was seeded in a 3 L jar fermenter (trade name: MDL-300model, manufactured by B.E. Marubishi Co., Ltd.) containing 1.8 L of thepreculture medium described above in a content of 1.0 v/v %. The culturewas performed for 28 hours in running conditions of a culturetemperature of 33° C., a stirring speed of 500 rpm, and an air flow rateof 1.8 L/minutes, while a pH was controlled to a range of 6.7 to 6.8.The pH was controlled by using a 7% aqueous ammonium hydroxide solution.

Next, a production culture of polyhydroxyalkanoate (PHA-2) was performedby seeding 5.0 v/v % of a pre-cultured mother seed in a 10 L jarfermenter (trade name: MDL-1000 model manufactured by B.E. MarubishiCo., Ltd.) containing 4.3 L of a production medium. The runningconditions were that a culture temperature was 28° C., a stirring speedwas 600 rpm, and an air flow rate was 6 L/minutes, and a pH wascontrolled to a range of 6.7 to 6.8. The pH was controlled by using a14% aqueous ammonium hydroxide solution. As a carbon source, palm kerneloil olein was poured in a specific substrate feed rate of 0.1 to 0.12 (goils and fats)×(g net dry strain weight)−1×(h)−1 over the whole medium.Here, the specific substrate feed rate is an amount of oils and fats fedto a unit weight of a net strain per unit time, i.e., a culture variabledefined as a pouring rate of oils and fats per a net dry strain weight.The net dry strain weight is a dry strain weight obtained by subtractinga contained polyester weight from the whole dry strain weight. Thespecific substrate feed rate is a value obtained from the above formula.In addition, an aqueous phosphate solution was continuously added afterthe culture was performed for 20 hours at a flow rate of a C/P ratio of250 to 350. The culture was performed for about 64 hours. After theculture was finished, the strains were recovered by centrifugation,washed with methanol, and lyophilized, and the dry strain weight wasmeasured.

To 1 g of the obtained dry strains was added 100 ml of chloroform, andthe mixture was stirred at room temperature for 24 hours to extractpolyhydroxyalkanoate from the strains. After the residue of the strainswas filtered, the resulting product was concentrated in an evaporatoruntil the amount was reached 30 ml, to which 90 ml of hexane wasgradually added, and the mixture was stirred gently for one hour. Aftera precipitate was filtered, it was dried in a vacuum at 50° C. for 3hours to obtain polyhydroxyalkanoate.

A composition analysis of the obtained polyhydroxyalkanoate was measuredaccording to a gas chromatography as shown below. To 20 mg of the drypolyhydroxyalkanoate were added 2 ml of sulfuric acid-methanol mixedliquid (15:85) and 2 ml of chloroform, and the mixture was sealed. Itwas heated at 100° C. for 140 minutes to obtain a methyl ester of thePHA decomposition product. It was cooled, to which 1.5 g of sodiumhydrogencarbonate was added little by little to neutralize it, and theresulting product was allowed to stand until the generation of carbonicacid gas was stopped. After 4 ml of diisopropyl ether was added theretoand the mixture was thoroughly mixed, the mixture was centrifuged, and amonomer unit composition of a polyester decomposition product in thesupernatant was analyzed by a capillary gas chromatography. GC-17A,manufactured by Shimadzu Corporation, was used as the gas chromatograph,and NEUTRA BOND-1, manufactured by GL Sciences Inc. (a column length: 25m, a column inside diameter: 0.25 mm, a liquid membrane thickness: 0.4μm), was used as the capillary column. Hexane was used as the carriergas, a column inlet pressure was 100 kPa, and 1 μl of a sample wasinjected. Temperature conditions were as follows: a temperature wasrisen from an initial temperature, 100° C. to 200° C. at a rate of 8°C./minute, followed by from 200° C. to 290° C. at a rate of 30°C./minute. As a result of the analysis under the conditions describedabove, the polyhydroxyalkanoate, obtained in Synthetic Example 1, waspoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH), and a molarratio of the 3-hydroxybutyrate (3HB) in that composition was 87% bymole.

The molecular weight of the obtained polyhydroxyalkanoate was obtainedby performing a gel permeation chromatography, as described below. In 10ml of chloroform was dissolved 15 mg of the extracted PHA, and thesolution was filtered through a 0.2 μm filter to obtain a sample formeasurement. Measurement was performed using 0.05 ml of the obtainedsample. SLC-10A (manufactured by Shimadzu Corporation) was used as themeasurement system, two columns of Shodex GPC K-806L (manufactured byShowa Denko K. K.) were attached thereto in series, and a temperature ofa column oven was set at 40° C. Chloroform was used as a mobile phase,and a flow rate was 1.0 ml/L. Detection was performed using an RIdetector (RID-10A manufactured by Shimadzu Corporation). As a referencestandard, polystyrenes (manufactured by Showa Denko K. K., a weightaverage molecular weight: about 7,000,000, about 1,070,000, 150,000, or30,000), which were treated in the same manner as the production of thesample for measurement, were used. Calibration curves were made based onthe measurement results of the reference standards, and a weight averagemolecular weight of a sample for measurement was calculated utilizingthe calibration curve. The obtained sample had a weight averagemolecular weight of 550,000.

In Synthetic Example 1, P3HB3HH (PHA-2) having a 3HB ratio of 87% bymole and a weight average molecular weight of 550,000 was obtained.

Synthetic Example 2 Synthesis of PHA-3

PHA-3 was obtained as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) inthe same manner as in Synthetic Example 1, except that the aqueousphosphate solution was continuously added at a flow rate of a C/P ratioof 600 to 800 after the culture was performed for 20 hours. In SyntheticExample 2, P3HB3HH (PHA-3) having a 3HB ratio of 89% by mole and aweight average molecular weight of 500,000 was obtained.

Synthetic Example 3 Synthesis of PHA-4

PHA-4 was obtained as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) inthe same manner as in Synthetic Example 2 except that KNK-005 strains(see U.S. Pat. No. 7,384,766) was used instead of KNK-631 strains, andpalm double olein oil was used as a carbon source. In Synthetic Example3, P3HB3HH (PHA-4) having a 3HB ratio of 94% by mole and a weightaverage molecular weight of 490,000 was obtained.

Synthetic Example 4 Synthesis of PHA-1

KNK-005 trc-phaJ4b.ΔphaZ1,2,6 strains were used for culture production.The strains were produced in a method described below.

First, plasmids for gene disruption were produced as follows: PCR wasperformed using genome DNA of Cupriavidus necator H16 strain as atemplate and primers represented by SEQ NO. 1 and SEQ NO. 2. PCR wasperformed by repeating 25 cycles of (1) at 98° C. for 2 minutes, and (2)at 98° C. for 15 seconds, at 60° C. for 30 seconds, and at 68° C. for 2minutes, and KOD-plus- (manufactured by Toyobo Co., Ltd.) was used as apolymerase. Similarly, PCR was performed using primers represented bySEQ NO. 3 and SEQ NO. 4. Further, using two kinds of DNA fragmentsobtained in the PCRs described above, as templates, PCR was performedusing primers represented by SEQ NO.1 and SEQ NO. 4 in the sameconditions as above, and the obtained DNA fragment was digested with arestriction enzyme SwaI. The DNA fragment was linked to a vectorpNS2X-sacB described in JP-A No.2007-259708, which was SwaI-digested,with DNA ligase (Ligation High, manufactured by Toyobo Co., Ltd.),thereby producing a plasmid vector for gene disruption pNS2X-phaZ6(−+),having base sequences on upstream and downstream the phaZ6 structuralgene.

Further, PCR was performed in the same manner as above using genome DNAof C. necator H16 strain as a template and primers represented by SEQNO. 5 and SEQ NO. 6. In addition, PCR was performed in the same manneras above using primers represented by SEQ NO. 7 and SEQ NO. 8.Furthermore, PCR was performed in the same manner as above using the twokinds of the DNA fragments, obtained in the PCRs above, as templates,and primers represented by SEQ NO. 5 and SEQ NO. 8, and the obtained DNAfragment was digested with the restriction enzyme SwaI. The DNA fragmentwas linked to vector pNS2X-sacB described in JP-A No. 2007-259708, whichwas SwaI-digested, with DNA ligase (Ligation High, manufactured byToyobo Co., Ltd.), thereby producing a plasmid vector for genedisruption pNS2X-phaZ1(−+) having DNA sequences on upstream anddownstream the phaZ1 structural gene.

Further, PCR was performed in the same manner as above using genome DNAof C. necator H16 strain as a template, and primers represented by SEQNO. 9 and SEQ NO. 10. In addition, PCR was performed in the same manneras above using primers represented by SEQ NO. 11 and SEQ NO. 12.Furthermore, PCR was performed in the same manner as above using the twokinds of the DNA fragments, obtained in the PCRs above, as templates,and primers represented by SEQ NO. 9 and SEQ NO. 12, and the obtainedDNA fragment was digested with restriction enzyme SwaI. The DNA fragmentwas linked to vector pNS2X-sacB described in JP-A No. 2007-259708, whichwas SwaI-digested, with DNA ligase (Ligation High, manufactured byToyobo Co., Ltd.), thereby producing a plasmid vector for genedisruption vector pNS2X-phaZ2(−+) having DNA sequences on upstream anddownstream the phaZ2 structural gene.

Next, gene-disrupted strains were produced. The plasmid vectors for genedisruption pNS2X-phaZ6(−+) were introduced into E. coli S17-1 strains(ATCC47055). The obtained E. coli strains and KNK005 strains (see U.S.Pat. No. 7,384,766) were subjected to mixed culture on a Nutrient Agarmedium (manufactured by Difco Inc.) to conjugate them. The KNK005 strainwas a strain which introduced a gene coding PHA synthase having an aminoacid sequence represented by SEQ NO. 19 in the sequence table to aCupriavidus necator 1-116 strain.

The culture medium was seeded in Simmons agar medium (sodium citrate 2g/L, sodium chloride 5 g/L, magnesium sulfate.7hydrate 0.2 g/L, ammoniumdihydrogen phosphate 1 dipotassium hydrogen phosphate 1 g/L, and agar 15g/L, pH 6.8) containing 250 mg/L of kanamycin, and strains grown on theagar medium were selected, thereby obtaining strains in which theplasmids were inserted onto chromosomes of the KNK005 strains. After thestrains were subjected to second generation cultivation in a NutrientBroth medium (manufactured by Difco Inc.), the obtained strains werediluted and coated on Nutrient Agar medium containing 15% saccharose,and grown strains were obtained as strains which were sloughed from theplasmids.

One strain having a deletion from a start codon to a stop codon of thephaZ6 genes on the chromosome was isolated from the obtained strainsaccording to the analysis by PCR, and the obtained gene disruptionstrain was designated as “KNK005 ΔphaZ6 strain.” Further, a chromosomegene disruption strain KNK005 ΔphaZ2,6 strain with a deletion from astart codon to a stop codon of the phaZ6 gene on the chromosome andfurther a deletion from the 16th codon to the stop codon on the phaZ2gene was produced in the same manner as above, using pNS2X-phaZ2(−+),with a KNK005.phaZ6 strain being a parent strain. Furthermore, a genedisruption strain KNK005 ΔphaZ1,2,6 strain with a deletion from a startcodon to a stop codon of the phaZ6 gene and further a deletion from the16th codon to the stop codon on the phaZ2 gene was produced in the samemanner as above, using pNS2X-phaZ1(−+), with a KNK005 ΔphaZ2,6 strainbeing a parent strain.

Next, a promoter and a plasmid for inserting Shine-Dalgarno sequence (SDsequence) were produced. PCR was performed using genome DNA of C.necator H16 strain as a template, and primers represented by SEQ NO. 13and SEQ NO. 14. In addition, PCR was performed in the same conditions asabove using primers represented by SEQ NO. 15 and SEQ NO. 16.Furthermore, PCR was performed in the same conditions as above usingplasmid pKK388-1(manufactured by Clontech Laboratories, Inc.) as atemplate and primers represented by SEQ NO. 17 and SEQ NO. 18.

PCR was performed in the same conditions as above using the three kindsof the DNA fragments obtained in the PCRs above as templates, and usingprimers represented by SEQ NO. 13 and SEQ NO. 16. The obtained DNAfragment was digested with restriction enzyme SwaI. The DNA fragment waslinked to vector pNS2X-sacB, described in JP-A No. 2007-259708, whichwas SwaI-digested, with DNA ligase (Ligation High, manufactured byToyobo Co., Ltd.), thereby producing a plasmid vector for inserting DNA,p-NS2X-sacB+phaJ4bU-trc-phaJ4b, having a base sequence having a regionupstream the phaJ4b structural gene, the trc promoter, the phaC1SDsequence, and the phaJ4b structural gene.

Next, a promoter and SD sequence-inserted strain were produced. Thepromoter and the plasmid vector for inserting SD sequence,pNS2X-sacB+phaJ4bU-trc-phaJ4b, were introduced into E. coli S17-1strains (ATCC47055) by transformation. The obtained E. coli strains andthe KNK005 ΔphaZ1,2,6 strains were subjected to mixed culture on aNutrient Agar medium (manufactured by Difco Inc.) to conjugate them.

The culture medium was seeded in Simmons agar medium (sodium citrate 2g/L, sodium chloride 5 g/L, magnesium sulfate.7hydrate 0.2 g/L, ammoniumdihydrogen phosphate 1 g/L, dipotassium hydrogen phosphate 1 g/L, andagar 15 g/L, pH 6.8) containing 250 mg/L of kanamycin, and strains grownon the agar medium were selected, thereby obtaining strains in which theplasmids were inserted onto chromosomes of the KNK005 ΔphaZ1,2,6strains. After the strains were subjected to second generationcultivation in a Nutrient Broth medium (manufactured by Difco Inc.), theobtained strains were diluted and coated on Nutrient Agar mediumcontaining 15% saccharose, and grown strains were obtained as strainswhich were sloughed from the plasmids.

Further, one strain, in which a DNA fragment having an expressionregulatory sequence containing a trc promoter and a phaClSD sequence,which was represented by SEQ NO. 20, was inserted at the upstream sideof phaJ4b structural gene on the chromosome, was isolated according tothe analysis by PCR. The obtained promoter and SD sequence-insertedstrain were designated as KNK005 trc-phaJ4b ΔphaZ1,2,6 strain. PHA-1 wasobtained as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) in the samemanner as in Synthetic Example 2 using the obtained KNK005 trc-phaJ4bΔphaZ1,2,6 strain. In Synthetic Example 4, P3HB3HH (PHA-1) having a 3HBratio of 80% by mole, and a weight average molecular weight of 520,000was obtained.

The molar ratios of 3-hydroxybutyrate (3HB) and the weight averagemolecular weights of PHA-1 to -4, obtained in Synthetic Examples 1 to 4are shown in Table 1.

Synthetic Examples 5 to 7 Synthesis ofpoly[(3-hydroxybutyrate)-co-(4-hydroxybutyrate)] (P3HB4HB)

Three kinds of P3HB4HB (PHA-5 to -7) were synthesized according to amethod described in JP-B No. H08-19227 using, as a producing strain,Ralstonia Eutropha H16 (ATCC17699, a former name: Alcaligenes EutrophusH16).

First, the strains were seeded in a medium in which 10 g of a yeastextract, 10 g of polypeptone, 5 g of a meat extract, and 5 g of ammoniumsulfate were dissolved in one liter of water and whose pH was 7, and itwas cultured at 30° C. The strains were fractionated from the obtainedculture medium by centrifugation. The obtained strains were seeded in anamount of 5 g based on one liter of a medium (pH 7) for synthesizingP3HB4HB, which was cultured at 30° C. for 48 hours, thereby obtaining aculture medium containing strains which accumulated P3HB4HB (PHA-5 to-7). As the medium for synthesizing P3HB4HB, three kinds of media wereused which were obtained by adding, as a carbon source, 5 parts of amixture of 2% by mole of γ-butyrolactone and 98% by mole of saccharose(Synthetic Example 5), a mixture of 3% by mole of γ-butyrolactone and97% by mole of saccharose (Synthetic Example 6), or a mixture of 5% bymole of γ-butyrolactone and 95% by mole of saccharose (Synthetic Example7) to 95 parts of a solution in which 39 nil of a 0.5 M aqueouspotassium hydrogen phosphate solution, 53.6 ml of a 0.5 M aqueousdipotassium hydrogen phosphate solution, 1 ml of a 20 w/v % aqueousmagnesium sulfate solution, and 1 ml of an mineral aqueous solution (Co,Fe, Ca, Ni, Cr, Ca, and the like) were dissolved in one liter ofdeionized water.

Each strain, obtained as above, was centrifuged, washed with distilledwater and acetone in this order, and dried in a reduced pressure toobtain a dry strain. P3HB4HB was extracted with hot chloroform from thedry strain, hexane was added to the obtained extract to precipitateP3HB4HB, and the precipitate was filtered and dried to obtain a polymerpreparation, P3HB4HB, as PHA-5 (Synthetic Example 5), PHA-6 (SyntheticExample 6), or PHA-7 (Synthetic Example 7). The molar ratios of3-hydroxybutyrate (3HB) and the weight average molecular weights ofthese polymers were shown in Table 2.

Synthetic Examples 8 to 12 Synthesis of (Meth)acrylate Resin by EmulsionPolymerization

In a pressure-resistant polymerization vessel equipped with athermometer, a stirrer, a reflux condenser, a nitrogen-introducinginlet, and a devise of adding monomers and emulsifiers were putdeionized water and sodium lauryl sulfate, and the mixture was heated to70° C. in nitrogen stream while it was stirred, to which potassiumpersulfate was added. After 30 minutes, deoxygenation underdecompression and pressurization with nitrogen were performed to have anappropriate dissolved oxygen concentration. After that, a monomermixture described in Table 2 was added at a rate of 25 parts/hour. Inaddition, 0.3 parts of sodium lauryl sulfate was added after 60 minutes,120 minutes, and 240 minutes from the start of the addition of themonomer mixture. After the addition of the monomer mixture was finished,the stirring was continued for one hour, and then 0.1 parts of sodiumformaldehyde sulfoxylate and 0.1 parts of tert-butyl peroxide wereadded. After that, the stirring was continued for one hour to obtain(meth)acrylate resin latex. The solid concentration of the obtainedlatex was adjusted to 40%. The number average primary particle size andthe weight average molecular weight of the (meth)acrylate resin wereadjusted to values described in Table 2, by controlling the initialamount (parts) of the sodium lauryl sulfate added, the amount of thepotassium persulphate added, and the dissolved oxygen concentration, andif necessary, adding tert-dodecyl mercaptan (a chain-transfer agent) tothe monomer mixture.

The latex having a solid concentration of 40%, obtained as above, wascoagulated with calcium chloride, granulated, dehydrated, and dried toprepare a white powdery (meth)acrylate resin. A theoretical glasstransition temperature, a number average particle size, a number averagemolecular weight, and a monomer composition of each of the(meth)acrylate resins obtained are shown in Table 2.

Synthetic Example 13 Synthesis of (Meth)acrylate Resin by SuspensionPolymerization

In a pressure-resistant polymerization vessel equipped with athermometer, a stirrer, a reflux condenser, a nitrogen-introducinginlet, and a devise of adding monomers and emulsions were put deionizedwater and 0.4 parts of tricalcium diphosphate, and the mixture washeated to 40° C. in nitrogen stream while it was stirred. After 30minutes, deoxygenation under decompression and pressurization withnitrogen were performed to have an appropriate dissolved oxygenconcentration. After that, 100 parts of a solution in which dilauroylperoxide was dissolved in a monomer mixture described in Table 2 wasadded thereto. After that, the stirring was continued for 30 minutes, towhich 0.25 parts of polyvinyl alcohol was added, and the stirring wascontinued for 30 minutes at the appropriate number of stirrings so as toobtain an appropriate liquid droplet particle size. After that, thegeneration of heat and the increase of a conversion, due to the geleffect, were confirmed, and then the polymerization temperature wasrisen to 80° C. and the stirring was continued until the conversionreached 97% or more, thereby obtaining a dispersion of a (meth)acrylateresin. The solid concentration of the dispersion was adjusted to 30%. Inaddition, the weight average molecular weight was adjusted to valuesdescribed in Table 2 by controlling the dissolved oxygen concentrationand the amount (parts) of the lauroyl peroxide added, and addingtert-dodecyl mercaptan (a chain-transfer agent) to the monomer mixture,and the number average primary particle size was adjusted to a valuedescribed in Table 2 by controlling the number of stirrings. Theobtained dispersion was dehydrated and dried to obtain a white powdery(meth)acrylate resin. A theoretical glass transition temperature, anumber average particle size, a number average molecular weight, and amonomer composition of the (meth)acrylate resins obtained are shown inTable 2.

The meaning of abbreviations of the (meth)acrylate resin in Table 2 isexplained based on the abbreviation “N220-57-0.3” of the methacrylateresin obtained in Synthetic Example 8. The abbreviation is formed of “N”which is a capital letter of the alphabet in a first position, “220” ina second position. “57” in a third position, and “0.3” in a fourthposition. The first position shows a polymerization method, and N showsan emulsion polymerization. In addition, there is also “K: suspensionpolymerization product” as the (meth)acrylate resin obtained inSynthetic Example 13. The second position shows a weight averagemolecular weight in terms of the polystyrene (unit: 0,000). The thirdposition shows a glass transition temperature (unit: ° C.). The fourthposition shows a number average primary particle size (unit: μm). Asdescribed above, the main properties of the (meth)acrylate resin can berevealed from its abbreviation.

Example 1 (1) Preparation Step of Vinyl Chloride Resin Compound

100 parts of a vinyl chloride resin was 4000 g. Into a Henschel mixer(Super Mixer SM, V20, manufactured by Kawata Mfg Co., Ltd.) was charged100 parts of a vinyl chloride resin (MB1008) described in Table 1, intowhich 2.0 parts of a butyltin-containing sulfur stabilizer (trade name:TVS #1360, manufactured by Nitto Kasei Co., Ltd.) was charged over oneminute in a low speed stirring mode. After that, steam was introducedinto a jacket of the mixer, and a high speed stirring mode was started.When the compound temperature reached 60° C., the stirring was oncesuspended, and 0.4 parts of a high molecular composite ester outerlubricant (trade name: Loxiol G70S manufactured by BASF Japan Co., Ltd.)and 0.5 parts of a polyol ester inner lubricant (trade name: Loxiol GH4,manufactured by BASF Japan Co., Ltd.) were charged into it. The highspeed stirring mode was started again, and when the compound temperaturereached 90° C., the stirring was once suspended and 1.0 part of a(meth)acrylate resin (N220-57-0.3) described in Table 2 was charged intoit. Again, the high speed stirring mode was started, and when thecompound temperature reached 105° C., the stirring was stopped. Afterthat, the introduction of the steam to the jacket was stopped, water wasintroduced to the jacket of the mixer, and the low speed stirring modewas started. The cooling was continued until the compound temperaturereached 80° C., and an outlet was opened and a compound was recovered.

(2) Preparation Step of Polyhydroxyalkanoate Compound

100 parts of polyhydroxyalkanoate was 4000 g. Into a Henschel mixer werecharged 100 parts of a polyhydroxyalkanoate (PHA-2) described in Table1, 0.4 parts of a high molecular composite ester outer lubricant (LoxiolG70S), 0.5 parts of a polyol ester inner lubricant (Loxiol GH4), and 1.0part of a (meth)acrylate resin (N220-57-0.3) described in Table 2, andthe stirring and mixing were performed at room temperature over oneminute in a high speed stirring mode. After that, an outlet was opened,thereby preparing a polyhydroxyalkanoate compound.

(3) Roll Forming Step

The total amount of 100 parts of the vinyl chloride resin and thepolyhydroxyalkanoate was 150 g. A test roll formed of a 8 inch-frontroll and a 8 inch-back roll was used, and a roll temperature was set at160° C., as described in Table 3. This roll temperature was atemperature at which the vinyl chloride resin compound was twined aroundthe roll in 30 seconds and a molded article was removed from the rollwithout any problem after finishing of the roll formation. The vinylchloride resin compound containing 20 parts of the vinyl chloride resinwas charged into the roll over 20 seconds under conditions that thenumber of revolutions of the front roll was 18 rpm and the number ofrevolutions of the back roll was 15 rpm. After the vinyl chloride resincompound was twined around the roll, it was kneaded for 2 minutes. Afterthat, the polyhydroxyalkanoate compound containing 80 parts of thepolyhydroxyalkanoate was charged over 20 seconds, and the kneading wasperformed for 4 minutes by width-aligning a sheet-like melted article,which was twined around the roll, from both right and left sides towardthe center using a bamboo stick. After 12 seconds from the completion ofthe kneading, the roll was stopped, and the molded article was cut intoa sheet, which was naturally cooled, thereby obtaining a sheet-likemolded article having a thickness of 0.3 mm.

(4) Press-Forming Step

The sheet-like molded article, obtained by the roll-forming, was cutinto multiple sheets, and they were put on top of each other, which wasput between heating presses whose temperature was set at a temperature5° C. higher than the roll temperature in the roll-forming describedabove, and it was pre-heated for 8 minutes. The pressure thereof wasincreased to 50 MPa for 30 seconds, and was kept as it was for 2minutes. After that, the pressure was released, and, immediately after,the pressed product was inserted into a cooling press machine. Apressure of 50 MPa was applied thereto, and it was cooled as it was for15 minutes, thereby obtaining a sheet-like molded article having athickness of 1.0 mm. The obtained molded article was subjected to ameasurement of each physical property.

Examples 2 to 5 and Comparative Examples 1 to 5

Sheet-like molded articles having a thickness of 1.0 mm were obtained,and they were subjected to the measurement of each physical property inthe same manner as in Example 1, except that the blending ratio of thevinyl chloride resin (MB1008) and the polyhydroxyalkanoate (PHA-2), theroll temperature in the roll forming step, and the press temperature inthe press-forming step were changed to values shown in Table 3.

Examples 6 to 8 and Comparative Examples 6 to 10

In the roll forming step, 5 parts (Example 6), 10 parts (Example 7), or15 parts (Example 8), the parts being based on the total amount 100parts of the vinyl chloride resin and the polyhydroxyalkanoate, of aglycerol plasticizer (trade name: RIKEMAL PL012, manufactured by RikenVitamin Co., Ltd.) was added to a vinyl chloride resin compoundcontaining 60 parts of the vinyl chloride resin, and they were added andmixed to prepare a vinyl chloride resin-containing compound. Sheet-likemolded articles of Examples 6 to 8, having a thickness of 1.0 mm, wereobtained in the same manner as in Example 5, except that the vinylchloride resin-containing compounds were used instead of the vinylchloride resin compound, and the roll temperature in the roll formingstep and the press temperature at the press-forming were changed totemperatures shown in Table 4. Molded articles of Comparative Examples 6to 10, having a thickness of 1.0 mm were obtained in the same manner asin Comparative Example 5, and they were subjected to the measurement ofeach physical property. The results from Example 5 and ComparativeExample 5 are provided again in Table 4. Form these results, it is foundthat the tensile elasticity of 1000 MPa or less and the tensileelongation of 100% or more which is defined as the soft thermoplasticresin in the present invention, can be shown within the range of thepresent invention, and the moldability with no problem Δ or more) andthe reduced plasticizer migration (3 or more) can be realized.

Comparative Examples 5 to 10 in Table 4 show examples in which theplasticizer was added to the vinyl chloride resin withoutpolyhydroxyalkanoate. It is found that either of the tensile elasticityof 1000 MPa, the tensile elasticity of 100% or more, and the reducedplasticizer migration (3 or more) cannot be obtained.

Examples 9 to 13 and Comparative Examples 11 to 13

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 5, except that the blending ratio (parts) of the(meth)acrylate resin was changed to values described in Table 5 and, inExamples 11 to 13 and Comparative Example 13, N100-57-0.3, obtained inSynthetic Example 9, was used as the (meth)acrylate resin, instead ofN220-57-0.3.

Examples 14 to 16 and Comparative Examples 14 to 18

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 5, except that, as the (meth)acrylate resin,instead of N220-57-0.3, N100-105-0.3 (Examples 14 to 16 and ComparativeExample 14) obtained in Synthetic Example 10, N12-57-0.3 (ComparativeExamples 15 and 16) obtained in Synthetic Example 12, or K100-57-50(Comparative Examples 17 and 18) obtained in Synthetic Example 13 wasused, and the blending ratio (parts) of the (meth)acrylate resin waschanged to values described in Table 6.

Examples 17 and 18 and Comparative Examples 19 and 20

Sheet-like molded articles having a thickness of 1.0 mm was obtained,and they were subjected to the measurement of each property in the samemanner as in Example 4, except that the blending ratio (parts) of the(meth)acrylate resin (N220-57-0.3) was changed to values described inTable 7, and the roll temperature 170° C. in the roll forming step andthe press temperature 175° C. in the press-forming step were changed to165° C. and 170° C., respectively.

Examples 19 to 21 and Comparative Examples 21 and 22

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 7, except that the blending ratio (parts) of the(meth)acrylate resin (N220-57-0.3) was changed to values described inTable 7, and the roll temperature 165° C. in the roll forming step andthe press temperature 170° C. in the press-forming step were changed to160° C. and 165° C., respectively.

Examples 22 to 24

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 4, except that PHA-1 (Example 22), PHA-3 (Example23), or PHA-4 (Example 24) was used as the polyhydroxyalkanoate, insteadof PHA-2, as shown in Table 8. In Table 8, Example 4 was provided again.

Examples 25 to 27

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 5, except that PHA-5 (Example 25), PHA-6 (Example26), or PHA-7 (Example 27) was used as the polyhydroxyalkanoate, insteadof PHA-2, as shown in Table 8. In Table 8, Example 5 was provided again.

Examples 28 to 30 and Comparative Example 23

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 5, except that S1008 (Example 28), S1001 (Example29), S1003 (Example 30), or KS2500 (Comparative Example 23) was used asthe vinyl chloride resin, instead of MB1.008, as shown in Table 9, andthe roll temperature in the roll forming step and the press temperaturein the press-forming step were changed to temperatures described inTable 9. In Table 9, Example 5 was provided again.

Examples 31 and 32

Sheet-like molded articles having a thickness of 1.0 mm were obtainedand they were subjected to the measurement of each property in the samemanner as in Example 5, except that, in the roll forming step, a vinylchloride resin compound containing 60 parts of a vinyl chloride resinand a polyhydroxyalkanoate compound containing 40 parts ofpolyhydroxyalkanoate were charged into a plastic bag, the bag wasvibrated for 60 seconds with hands at a rate of three times per second,the obtained blend was charged into the roll over 40 second, and it waskneaded for 6 minutes.

Tables 5 to 7 show examples in which the kind and addition amount(parts) of the (meth)acrylate resin in Comparative Examples 11 to 22,Example 5, and Examples 9 to 21 are changed. From these results, it isfound that the processability with no problem can be obtained, and thetensile elasticity of 1000 MPa or less, the tensile elongation of 100%or more, and the excellent reduced plasticizer migration (3 or more) areshown within the range of the present invention.

In Example 4, Example 5, and Examples 22 to 27 in Table 8, the kind ofthe polyhydroxyalkanoate and the copolymerization composition ratio werechanged. In addition, in Example 5, Examples 28 to 30, and ComparativeExample 23 in Table 9, the degree of polymerization of the vinylchloride resin was changed, and further in Example 5, Example 28,Example 31, and Example 32 in Table 9, the molding method was changed.It is found that the tensile elasticity of 1000 MPa or less, the tensileelongation of 100% or more, and the excellent reduced plasticizermigration (3 or more) are shown within the range of the presentinvention.

Examples 33 to 36 and Examples 39 and 40 (1) Preparation Step of FirstStage Compound

100 parts was 4000 g. To a Henschel mixer (Super Mixer SM V20,manufactured by Kawata Mfg Co., Ltd.) was charged 60 parts of a vinylchloride resin (S1001, S1008, or MB1008) described in Table 10, intowhich 3.0 parts of a barium-zinc stabilizer (trade name: AC-186,manufactured by ADEKA Corporation) was charged over one minute in a lowspeed stirring mode. After that, steam was introduced into a jacket ofthe mixer, and a high speed stirring mode was started. When the compoundtemperature reached 60° C., the stirring was once suspended, and 0.4parts of a high molecular composite ester outer lubricant (trade name:Loxiol G70S, manufactured by BASF Japan Co., Ltd.) and 0.5 parts oferucic acid amide (trademark: NEUTRON-S, manufactured by Nippon FineChemical Co., Ltd.) were charged into it. The high speed stirring modewas started again, and when the compound temperature reached 90° C., thestirring was once suspended and 3.0 parts of a (meth)acrylate resin(N220-57-0.3) and polyhydroxyalkanoate (PHA-2), which was used as thefirst stage compound, described in Table 10, were charged into it.Again, the high speed stirring mode was started, and when the compoundtemperature reached 105° C., the stirring was stopped. After that, theintroduction of the steam to the jacket was stopped, water wasintroduced to the jacket of the mixer, and the low speed stirring modewas started. The cooling was continued until the compound temperaturereached 80° C., and an outlet was opened and a first stage compound wasrecovered.

(2) Pre-Kneading Step (Preparation Step of Second Stage Compound)

A mixer with an air cooling function (trade name: Roller Mixer R60Model, manufactured by Toyo Seiki Seisaku-Sho Ltd.) was attached to akneading evaluation machine (trade name: Labo Plasto Mill C, Type: Model50C 150, manufactured by Toyo Seiki Seisaku-Sho Ltd.), which was used asa small-sized machine of a Banbury mixer. 100 parts was 66 g. The mixertemperature of the machine was adjusted to 100° C., and the whole amountof the first stage compound, obtained as above, was charged to themachine while inching was performed. After the completion of thecharging, pre-heating was performed for one minute, and rotation ofroller was started. After the starting of the rotation, the number ofrevolutions was increased to 100 rpm over one minute, and then thenumber of revolutions was kept at 100 rpm. When a resin thermometershowed 155° C., the rotation was once stopped, and polyhydroxyalkanoate(PHA-2), which was used as the second stage compound, was charged whilethe inching was performed. After that, the rotation was started again ata rate of 100 rpm, and a compound after the pre-kneading was dischargedat a stage at which the resin thermometer showed 155° C. again. Theoperation described above was performed using the three same machines,which were aligned in parallel, thereby obtaining 198 g, correspondingto 3 times amount of 66 g, of the second stage compound.

(3) Roll Forming Step 1

A test roll formed of a 8 inch-front roll and a 8 inch-back roll wasused as a mixing roll, and the number of revolutions of the front rollwas adjusted to 25 rpm, the number of revolutions of the back roll wasadjusted to 23 rpm, and a space between the rolls was adjusted to 0.5mm. A roll temperature was set at 165° C. (Example 40), 170° C. (Example39), or 175° C. (Examples 33 to 37), as described in Table 10. Thesecond stage compound, obtained in the pre-kneading step, was chargedinto the roll after one minute from the completion of the pre-kneadingstep to wind it around the roll, and kneading was performed for 3minutes by width-aligning a sheet-like melted article from both rightand left sides toward the center using a bamboo stick. After that, whilethe width-aligning was continued, a 3 cm-central part was cut into“strip” and it was continuously transported to a roll forming step 2.

(4) Roll Forming Step 2

The same test roll as used in (3) was used as a calendar roll, and thenumbers of the revolutions were adjusted as the same as (3). The rolltemperature was adjusted to a temperature of the roll temperature in theroll forming step 1-10° C., as described in Table 10, the melted resin“strip,” transported from the roll forming step 1, was twined around theroll, and a space between the rolls was adjusted so that a thickness ofa sheet was 0.15 mm. After that, the sheet-like melted product was cutinto to obtain a sheet-like molded article.

(5) Press-Forming Step

The step was performed in the same manner as in Example 1.

(6) Evaluation

An adhesion to roll, a transportability of melted resin, and atransparency were evaluated based on the following criteria. The airmark, the flow mark, and the particle were evaluated in the same manneras in Example 1, and the tensile test and the plasticizer igration testwere performed in the same manner as in Example 1 except that “0.15mm-sheet-like molded article obtained in Roll Forming Step 2” was usedinstead of the “sheet-like molded article having a thickness of 1.0 mmobtained in the press-forming.”

<Transportablity of Melted Resin>

The transportablity of melted resin is an indicator of an easiness oftransportation when the melted resin “strip” cut in the forming step 1is transported to the roll forming step 2.

⊚: The melted resin had appropriate rn_elt-viscosity and melt tension,and there was no problem in the transportation.

∘: The melted resin was lower in the melt-viscosity and the melttension, but the transportation could be done.

Δ: The melted resin was too low in the melt-viscosity and the melttension, but the transportation could be managed.

x: The melted resin was so low in the melt-viscosity and the melttension that the melted resin “strip” was too much elongated, and it wasdifficult to transport.

<Adhesion to Roll>

The adhesion to roll is an indication of easiness of the removal fromthe metal surface of the roll when the sheet-like melted resin was cutin the roll forming step 2.

⊚: The sheet-like melted resin was removed without any resistance.

∘: The sheet-like melted resin was removed without any problem.

Δ: The sheet-like melted resin was removed, although there were someresistances.

x: The sheet-like melted resin adhered to the metal surface of the roll,and could not be removed.

<Transparency>

∘: The sheet-like molded article was colorless and transparent, and abackground can be clearly seen.

Δ: The sheet-like molded article was somehow transparent, and abackground is seen unclearly.

x: The sheet-like molded, article was clouded, and it is difficult tosee a background.

Examples 37 and 38

Sheet-like molded articles were produced and the evaluations thereofwere performed in the same manner as in Example 33, except that vinylchloride resins described in Table 10 were used, the roll temperatureand the press temperature were adjusted to temperatures described inTable 10, and the pre-kneading step (2) (the preparation step of secondstage compound) was performed as follows.

(2) Pre-Kneading Step

A small-sized machine of a Banbury mixer, which was the same as inExample 33, was used. 100 parts was 66 g. A mixer temperature of themachine was adjusted to 100° C., and the whole amount of a first stagecompound was charged while inching was performed. After the completionof the addition, pre-heating was performed for one minute, and therotation of the roller was started. After the rotation was started, thenumber of revolutions was increased to 100 rpm over one minute and thenrotation was kept at 100 rpm. However, a resin thermometer did not reach155° C. even after 10 minutes. Subsequently, the second stage compound,polyhydroxyalkanoate (PHA-2), was charged. After that, the rotation wasstarted at 100 rpm again, and a second stage compound was discharged ata stage at which the resin thermometer showed 155° C. again. Theoperation described above was performed using the three same machines,which were aligned in parallel, thereby obtaining 1.98 g, correspondingto 3 times amount of 66 g, of the compound after the pre-kneading.

In comparison of Examples 33 to 37, the sheet-like molded articleshaving both of the physical properties and the moldability at highlevels can be obtained by the addition of 5 to 30 parts (12.5 to 75% ofthe whole blending amount) of polyhydroxyalkanoate to the first stagecompound. It is found from the comparison of Example 35 and Examples 38to 40 that the vinyl chloride resin, which is the homopolymer, and has adegree of polymerization of 750 or more and 1200 or less, particularly900 to 1200 is good.

TABLE 1 Product name Abbreviation Name Maker Detail Kanevinyl MB 1008MB1008 Vinyl chloride resin Kaneka Corporation Degree of polymerization≈ 680, Copolymer Vinyl acetate content = 10% by weight Kanevinyl S1008S1008 Vinyl chloride resin Kaneka Corporation Degree of polymerization ≈800, Homopolymer Kanevinyl S1001 S1001 Vinyl chloride resin KanekaCorporation Degree of polymerization ≈ 1050, Homopolymer Kanevinyl S1003S1003 Vinyl chloride resin Kaneka Corporation Degree of polymerization ≈1300, Homopolymer Kanevinyl KS2500 KS2500 Vinyl chloride resin KanekaCorporation Degree of polymerization ≈ 2500, Homopolymer SynthesisExample 1 PHA-2 Polyhydroxyalkanoate Kaneka Corporation P3HB3HH⁽¹⁾ Ratioof 3HB⁽³⁾ = 87% by mole, Weight average molecular weight = 550,000Synthesis Example 2 PHA-3 Polyhydroxyalkanoate Kaneka CorporationP3HB3HH⁽¹⁾ Ratio of 3HB⁽³⁾ = 89% by mole, Weight average molecularweight = 500,000 Synthesis Example 3 PHA-4 Polyhydroxyalkanoate KanekaCorporation P3HB3HH⁽¹⁾ Ratio of 3HB⁽³⁾ = 94% by mole, Weight averagemolecular weight = 490,000 Synthesis Example 4 PHA-1Polyhydroxyalkanoate Kaneka Corporation P3HB3HH⁽¹⁾ Ratio of 3HB⁽³⁾ = 80%by mole, Weight average molecular weight = 520,000 Synthesis Example 5PHA-5 Polyhydroxyalkanoate Kaneka Corporation P3HB4HB⁽²⁾ Ratio of 3HB⁽³⁾= 92% by mole, Weight average molecular weight = 710,000 SynthesisExample 6 PHA-6 Polyhydroxyalkanoate Kaneka Corporation P3HB4HB⁽²⁾ Ratioof 3HB⁽³⁾ = 86% by mole, Weight average molecular weight = 1,010,000Synthesis Example 7 PHA-7 Polyhydroxyalkanoate Kaneka CorporationP3HB4HB⁽²⁾ Ratio of 3HB⁽³⁾ = 79% by mole, Weight average molecularweight = 990,000 ⁽¹⁾P3HB3HH:Poly(3-hydroxybutyrate)-co-(3-hydroxyhexanoate) ⁽²⁾P3HB4HB:Poly(3-hydroxybutyrate)-co-(4-hydroxybutyrate) ⁽³⁾3HB: 3-Hydroxybutyrate

TABLE 2 Product name Abbreviation Name Maker Detail SynthesisN220-57-0.3 Methacrylate resin Kaneka Emulsion polymerization product,Theoretical Tg = 57° C., Example 8 Corporation Number average particlesize = 0.3 μm, Molecular weight = 2,200,000, Composition MMA/BA =80/20⁽⁴⁾ Synthesis N100-57-0.3 Methacrylate resin Kaneka Emulsionpolymerization product, Theoretical Tg = 57° C., Example 9 CorporationNumber average particle size = 0.3 μm, Molecular weight = 1,000,000,Composition MMA/BA = 80/20⁽⁴⁾ Synthesis N100-105-0.3 Methacrylate resinKaneka Emulsion polymerization product, Theoretical Tg = 105° C.,Example 10 Corporation Number average particle size = 0.3 μm, Molecularweight = 1,000,000, Composition MMA/BA = 100/0⁽⁴⁾ Synthesis N100-135-0.3Methacrylate resin Kaneka Emulsion polymerization product, TheoreticalTg = 135° C., Example 11 Corporation Number average particle size = 0.3μm, Molecular weight = 1,000,000, Composition MMA/MAA = 70/30⁽⁴⁾Synthesis N12-57-0.3 Methacrylate resin Kaneka Emulsion polymerizationproduct, Theoretical Tg = 57° C., Example 12 Corporation Number averageparticle size = 0.3 μm, Molecular weight = 120,000, Composition MMA/BA =80/20⁽⁴⁾ Synthesis K100-57-50 Methacrylate resin Kaneka Suspensionpolymerization product, Theoretical Tg = 57° C., Example 13 CorporationNumber average particle size = 50 μm, Molecular weight = 1,000,000,Composition MMA/BA = 80/20⁽⁴⁾ TVS# 1360 TVS#1360 Butyltin-containingNitto Kasei Pale yellow liquid, Refractive index = 1.502 to 1.508,sulfur stabilizer Co., Ltd. Specific gravity = 1.118 to 1.138 (quotedfrom a maker's catalog) Loxiol G70S G70S High molecular BASF JapanSolid, Coagulation point: 55 to 58° C. (quoted from a maker's catalog)composite ester Co., Ltd outer lubricant Loxiol GH4 GH4 Polyol esterinner BASF Japan Solid, Coagulation point: 75 to 80° C. (quoted from amaker's catalog) lubricant Co., Ltd Rikemal PL012 PL012 Glycerolplasticizer Riken Vitamin Glycerol diacetomonolaurate, Pale yellowliquid, Degree of Co., Ltd. acetylation ? 95% (quoted from a maker'scatalog) ⁽⁴⁾MMA: Methyl methacrylate, BA: Butyl acrylate, MAA,Methacrylic acid

TABLE 3 Compar- Compar- Compar- Compar- Compar- ative Exam- Exam- Exam-Exam- Exam- ative ative ative ative Item Example 1 ple 1 ple 2 ple 3 ple4 ple 5 Example 2 Example 3 Example 4 Example 5 Blend- Vinyl ProductMB1008 MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 ingchloride name resin parts 0.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0100.0 Poly- Product PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2PHA-2 hydroxy- name alkanoate parts 100.0 80.0 70.0 60.0 50.0 40.0 30.020.0 10.0 0.0 (Meth)ac- Product N220- N220- N220- N220- N220- N220-N220- N220- N220- N220- rylate name 57-0.3 57-0.3 57-0.3 57-0.3 57-0.357-0.3 57-0.3 57-0.3 557-0.3 57-0.3 resin parts 1.0 1.0 1.0 1.0 1.0 1.01.0 1.0 1.0 1.0 Plasticizer Product name parts 0.0 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 Mold- Roll ° C. 150 160 165 165 170 170 170 170 170 170ing temper- ature Press ° C. 155 165 170 170 175 175 175 175 175 175temper- ature Physical HAZE % 65.4 36.2 29.8 8.7 3.2 3.1 2.2 2.3 2.6 2.8property Tensile MPa 11 20 8 13 28 27 71 81 70 31 breaking stressTensile % 64 764 576 442 324 312 5 6 5 32 break elongation Tensile MPa472 437 17 45 259 735 1992 1890 1853 1885 elasticity Plasticizer Rank 44 4 4 4 4 4 4 4 4 migration Mold- Air mark Rank Δ Δ Δ Δ Δ Δ Δ Δ Δ Δability Flow mark Rank ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Particle Rank ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯◯ ◯

TABLE 4 Compar- Compar- Compar- Compar- Compar- Compar- ative ativeative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam-Exam- Exam- Item ple 5 ple 6 ple 7 ple 8 ple 5 ple 6 ple 7 ple 8 ple 9ple 10 Blend- Vinyl Product MB1008 MB1008 MB1008 MB1008 MB1008 MB1008MB1008 MB1008 MB1008 MB1008 ing chloride name resin parts 60.0 60.0 60.060.0 100.0 100.0 100.0 100.0 100.0 100.0 Poly- Product PHA-2 PHA-2 PHA-2PHA-2 hydroxy- name alkanoate parts 40.0 40.0 40.0 40.0 0.0 0.0 0.0 0.00.0 0.0 (Meth)ac- Product N220- N220- N220- N220- N220- N220- N220-N220- N220- N220- rylate name 57-0.3 57-0.3 57-0.3 57-0.3 57-0.3 57-0.357-0.3 57-0.3 57-0.3 57-0.3 resin parts 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.01.0 1.0 Plasticizer Product PL012 PL012 PL012 PL012 PL012 PL012 PL012PL012 name parts 0.0 5.0 10.0 15.0 0.0 10.0 15.0 20.0 25.0 30.0 Mold-Roll ° C. 170 165 165 160 170 165 165 165 165 160 ing temper- aturePress ° C. 175 170 170 165 175 170 170 170 170 165 temper- aturePhysical HAZE % 3.1 3.7 3.2 8.5 2.8 3.2 2.0 2.7 2.7 3.0 property TensileMPa 27 18 12 9 31 26 32 29 21 19 breaking stress Tensile % 312 347 336315 32 53 164 206 235 287 break elongation Tensile MPa 735 171 10 7 18851647 1263 541 182 67 elasticity Plasticizer Rank 4 4 3 3 4 3 3 1 1 1migration Mold- Air mark Rank Δ Δ Δ Δ Δ Δ Δ Δ Δ Δ ability Flow mark Rank◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Particle Rank ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

TABLE 5 Compar- Compar- Compar- ative Exam- Exam- Exam- ative Exam-Exam- Exam- ative Item Example 11 ple 5 ple 9 ple 10 Example 12 ple 11ple 12 ple 13 Example 13 Blend- Vinyl Product MB1008 MB1008 MB1008MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 ing chloride name resin parts60.0 60.0 60.0 60.0 60.0 60.0 60.0 60.0 60.0 Poly- Product PHA-2 PHA-2PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 hydroxy- name alkanoate parts40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 (Meth)ac- Product N220-N220- N220- N220- N100- N100- N100- N100- rylate name 57-0.3 57-0.357-0.3 57-0.3 57-0.3 57-0.3 57-0.3 57-0.3 resin parts 0.0 1.0 3.0 6.09.0 1.0 3.0 6.0 9.0 Plasticizer Product name parts 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 Mold- Roll ° C. 170 170 170 170 170 170 170 170 170 ingtemper- ature Press ° C. 175 175 175 175 175 175 175 175 175 temper-ature Physical HAZE % 1.9 3.1 4.0 9.6 2.9 11.9 40.0 property Tensile MPa31.8 27 29.6 19.7 28.5 29.2 26.6 breaking stress Tensile % 297 312 282152 281 311 283 break elongation Tensile MPa 854 735 781 853 801 599 432elasticity Plasticizer Rank 4 4 4 4 4 4 4 migration Mold- Air mark RankX Δ ⊚ ⊚ ⊚ Δ ⊚ ⊚ ⊚ ability Flow mark Rank ◯ ◯ ◯ Δ X ◯ ◯ Δ X Particle Rank◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

TABLE 6 Compar- Compar- Compar- Compar- Compar- Exam- Exam- Exam- ativeative ative ative ative Item ple 14 ple 15 ple 16 Example 14 Example 15Example 16 Example 17 Example 18 Blend- Vinyl Product MB1008 MB1008MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 ing chloride name resin parts60.0 60.0 60.0 60.0 60.0 60.0 60.0 60.0 Poly- Product PIIA-2 PIIA-2PIIA-2 PIIA-2 PIIA-2 PIIA-2 PIIA-2 PIIA-2 hydroxy- name alkanoate parts40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 (Meth)ac- Product N100- N100-N100- N100- N12- N12- K100- K100- rylate name 105-0.3 105-0.3 105-0.3105-0.3 57-0.3 57-0.3 57-50 57-50 resin parts 1.0 3.0 6.0 9.0 3.0 6.03.0 6.0 Plasticizer Product name parts 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0Mold- Roll ° C. 170 170 170 170 170 170 170 170 ing temper- ature Press° C. 175 175 175 175 175 175 175 175 temper- ature Physical HAZE % 3.612.3 43.9 property Tensile MPa 29.7 30.0 27.6 breaking stress Tensile %268 302 271 break elongation Tensile MPa 816 606 454 elasticityPlasticizer Rank 4 4 4 migration Mold- Air mark Rank Δ ⊚ ⊚ ⊚ X X X Xability Flow mark Rank ◯ ◯ Δ X ◯ ◯ ◯ ◯ Particle Rank ◯ Δ Δ X ◯ ◯ X X

TABLE 7 Compar- Compar- Compar- Compar- ative Exam- Exam- ative ativeExam- Exam- Exam- ative Item Example 19 ple 17 ple 18 Example 20 Example21 ple 19 ple 20 ple 21 Example 22 Blend- Vinyl Product MB1008 MB1008MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 ing chloride name resinparts 50.0 50.0 50.0 50.0 60.0 60.0 60.0 60.0 60.0 Poly- Product PHA-2PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 hydroxy- name alkanoateparts 50.0 50.0 50.0 50.0 40.0 40.0 40.0 40.0 40.0 (Meth)ac- ProductN220- N220- N220- N220- N220- N220- N220- rylate name 57-0.3 57-0.357-0.3 57-0.3 57-0.3 57-0.3 57-0.3 resin parts 0.0 3.0 6.0 9.0 0.0 1.03.0 6.0 9.0 Plasticizer Product PL012 PL012 PL012 PL012 PL012 name parts0.0 0.0 0.0 0.0 10.0 10.0 10.0 10.0 10.0 Mold- Roll ° C. 165 165 165 165160 160 160 160 160 ing temper- ature Press ° C. 170 170 170 170 165 165165 165 165 temper- ature Physical HAZE % 10.0 24.6 2.8 2.8 4.7 6.9 11.7property Tensile MPa 20.3 23.0 9.7 10.6 11.9 11.9 12.3 breaking stressTensile % 369 403 339 309 322 294 297 break elongation Tensile MPa 225180 8 17 24 24 49 elasticity Plasticizer Rank 4 4 4 4 4 migration Mold-Air mark Rank X Δ ⊚ ⊚ X Δ ⊚ ⊚ ⊚ ability Flow mark Rank ◯ ◯ ◯ X ◯ ◯ ◯ ◯ XParticle Rank ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

TABLE 8 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Item ple 22 ple4 ple 23 ple 24 ple 5 ple 25 ple 26 ple 27 Blend- Vinyl Product MB1008MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 MB1008 ing chloride name resinparts 50.0 50.0 50.0 50.0 60.0 60.0 60.0 60.0 Poly- Product PHA-1 PHA-2PHA-3 PHA-4 PHA-2 PHA-5 PHA-6 PHA-7 hydroxy- name alkanoate parts 50.050.0 50.0 50.0 40.0 40.0 40.0 40.0 (Meth)ac- Product N220- N220- N220-N220- N220- N220- N220- N220- rylate name 57-0.3 57-0.3 57-0.3 57-0.357-0.3 57-0.3 57-0.3 57-0.3 resin parts 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Plasticizer Product name parts 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Mold-Roll ° C. 170 170 170 170 170 170 170 170 ing temper- ature Press ° C.175 175 175 175 175 175 175 175 temper- ature Physical HAZE % 2.3 3.214.3 40.2 3.1 54.2 42.5 18.3 property Tensile MPa 28 28 24 22 27 24 2927 breaking stress Tensile % 425 324 376 347 312 182 337 336 breakelongation Tensile MPa 103 259 378 232 735 834 509 361 elasticityPlasticizer Rank 4 4 4 4 4 4 4 4 migration Mold- Air mark Rank Δ Δ Δ Δability Flow mark Rank ◯ ◯ ◯ ◯ Particle Rank ◯ ◯ ◯ ◯

TABLE 9 Compar- Exam- Exam- Exam- Exam- ative Exam- Exam- Exam- Exam-Item ple 5 ple 28 ple 29 ple 30 Example 23 ple 28 ple 31 ple 5 ple 32Blend- Vinyl Product MB1008 S1008 S1001 S1003 KS2500 S1008 S1008 MB1008MB1008 ing chloride name resin parts 60.0 60.0 60.0 60.0 60.0 60.0 60.060.0 60.0 Poly- Product PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2PHA-2 hydroxy- name alkanoate parts 40.0 40.0 40.0 40.0 40.0 40.0 40.040.0 40.0 (Meth)ac- Product N220- N220- N220- N220- N220- N220- N220-N220- N220- rylate name 57-0.3 57-0.3 57-0.3 57-0.3 57-0.3 57-0.3 57-0.357-0.3 57-0.3 resin parts 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Plasticizer Product name parts 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Mold-Roll ° C. 170 180 190 195 200 180 180 170 170 ing temper- ature Press °C. 175 185 195 200 205 185 185 175 175 temper- ature Physical HAZE % 3.112.2 98.8 99.9 * 12.2 97.2 3.1 3.8 property Tensile MPa 27 27.0 29.632.2 27.0 35.5 27 28 breaking stress Tensile % 312 301 308 130 301 243312 286 break elongation Tensile MPa 735 762 928 989 762 867 735 751elasticity Plasticizer Rank 4 4 4 4 4 4 4 4 migration Mold- Air markRank ability Flow mark Rank Particle Rank * Molding impossible: Thevinyl chloride resin did not gel.

TABLE 10 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Item ple 33 ple34 ple 35 ple 36 ple 37 ple 38 ple 39 ple 40 Blending First stage VinylProduct S1001 S1001 S1001 S1001 S1001 S1003 S1008 MB1008 (Compound)chloride name resin parts 60.0 60.0 60.0 60.0 60.0 60.0 60.0 60.0 Poly-Product PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 PHA-2 hydroxy- namealkanoate parts 40.0 25.7 15.0 6.7 0.0 15.0 15.0 15.0 (Meth)ac- ProductN220- N220- N220- N220- N220- N220- N220- N220- rylate name 57-0.357-0.3 57-0.3 57-0.3 57-0.3 57-0.3 57-0.3 57-0.3 resin parts 3.0 3.0 3.03.0 3.0 3.0 3.0 3.0 Plasticizer Product name parts 0.0 0.0 0.0 0.0 0.00.0 0.0 0.0 Second Stage Poly- Product PHA-2 PHA-2 PHA-2 PHA-2 PHA-2PHA-2 PHA-2 PHA-2 hydroxy- name alkanoate parts 0.0 14.3 25 33.3 40.025.0 25.0 25.0 Molding Roll temperature ° C. 175 175 175 175 175 185 170165 Press temperature ° C. 180 180 180 180 180 190 175 170 PhysicalTransparency Rank X Δ ◯ ◯ X X ◯ ◯ property Tensile breaking stress MPa28.2 27.1 27.6 27.3 28.6 29.1 26.9 26.7 Tensile break elongation % 248295 287 302 254 221 309 301 Tensile elasticity MPa 852 721 715 734 868891 736 729 Plasticizer migration Rank 4 4 4 4 4 4 4 4 MoldabilityTransportability of melted resin Rank ⊚ ◯ ◯ ◯ ⊚ ⊚ Δ Δ Adhesion to rollRank ⊚ ◯ ◯ ◯ ⊚ ⊚ ◯ Δ Air mark Rank X ◯ ◯ ◯ X X ◯ ◯ Flow mark Rank ◯ ◯ ◯◯ ◯ ◯ ◯ ◯ Particle Rank ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

1: A soft thermoplastic resin composition comprising: 100 parts byweight of a resin component (A) containing 15 to 65 parts by weight of avinyl chloride resin having a degree of polymerization of 2000 or less,and 35 to 85 parts by weight of a polyhydroxyalkanoate; and 0.1 to 8parts by weight of a resin component (B) which is one or more resinsselected from the group consisting of a (meth)acrylate resin and anacrylonitrile-styrene resin, and has a weight average molecular weight,in terms of the polystyrene, of 400,000 or more.
 2. The softthermoplastic resin composition according to claim 1, wherein thepolyhydroxyalkanoate is a copolymer formed of monomer units derived fromtwo or more kinds of hydroxyalkanoates.
 3. The soft thermoplastic resincomposition according to claim 2, wherein the copolymer comprisesmonomer units derived from 3-hydroxybutyrate, and monomer units derivedfrom hydroxyalkanoate other than 3-hydroxybutyrate.
 4. The softthermoplastic resin composition according to claim 3, wherein thehydroxyalkanoate other than 3-hydroxybutyrate is at least one memberselected from the group consisting of 4-hydroxybutyrate,3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, and3-hydroxydecanoate.
 5. The soft thermoplastic resin compositionaccording to claim 3, wherein the copolymer contains 50 to 95% by moleof monomer units derived from the 3-hydroxybutyrate.
 6. The softthermoplastic resin composition according to claim 1, wherein the resincomponent (B) has a number average primary particle size of 40 μm orless.
 7. The soft thermoplastic resin composition according to claim 1,wherein a molded article therefrom having a thickness of 1 mm has anHAZE of 50% or less.
 8. A molded article comprising the softthermoplastic resin composition according to claim
 1. 9. A film or sheetcomprising the molded article according to claim 8.